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ava Drilling Fluids & Services

Drilling Fluids
Manual








ava S.p.A.
Via Salaria, 1313/C
00138 Rome, Italy

Tel: +39 06 8856111
Email: avaspa@avaspa.it
Internet: www.avaspa.it

Version 1
November 2004

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This manual is provided without warranty of any kind, either expressed or
implied. The information contained in this manual is believed to be
accurate, however AVA S.p.A, Newpark Drilling Fluids, LLC and any of its
affiliates, will not be held liable for any damages, whether direct or indirect
which result from the use of any information contained herein. Furthermore,
nothing contained herein shall be construed as a recommendation to use any
product in conflict with existing patents covering any materials or uses.

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TABLE OF CONTENTS


CHAPTER 1 GENERAL DUTIES AND FUNCTIONS OF DRILLING FLUIDS
CHAPTER 2 BASIC CHEMISTRY
CHAPTER 3 GEOLOGY
CHAPTER 4 CLAY CHEMISTRY AND PROPERTIES
CHAPTER 5 POLYMER CHEMISTRY
CHAPTER 6 FLUID LOSS CONTROL
CHAPTER 7 WATER BASED FLUIDS
CHAPTER 8 OIL BASED FLUIDS
CHAPTER 9 BOREHOLE STABILITY
CHAPTER 10 FLUID DESIGN
CHAPTER 11 SOLIDS CONTROL
CHAPTER 12 UNDERBALANCED DRILLING AND FOAM
CHAPTER 13 RHEOLOGY
CHAPTER 14 PRODUCTION ZONE DRILLING
CHAPTER 15 CORROSION
CHAPTER 16 PROBLEM SOLVING WITH DRILLING FLUIDS


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CHAPTER 1

GENERAL RIG DUTIES AND FUNCTIONS OF DRILLING FLUIDS


1.1 KEY POINTS AND SUMMARY

1.2 ROTARY DRILLING TECHNIQUE - INTRODUCTION TO DRILLING FLUIDS

1.3 PRINCIPLE FUNCTIONS OF DRILLING FLUIDS
1.3.1 Improve Cuttings Removal Rates
1.3.2 Control Sub-surface Pressures
1.3.3 Suspend and Release Solids
1.3.4 Maintain Borehole Stability
1.3.5 Protect Producing Formations
1.3.6 Control Corrosion Rates
1.3.7 Seal the Wall of the Borehole
1.3.8 Aid in Maximizing Penetration Rates
1.3.9 Aid in the Retrieval and Interpretation of Formation Data
1.3.10 Cool and Lubricate the Bit and Drill String
1.3.11 Other Functions

1.4 COMPOSITION OF DRILLING FLUIDS

1.5 PROPERTIES OF DRILLING FLUIDS

1.6 DUTIES AND RESPONSIBLITIES OF A MUD ENGINEER

REFERENCES
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1.1 KEY POINTS AND SUMMARY

Drilling Fluids Technology is continually changing and improving. These changes are usually
initiated by the need to improve drilling and production economics. Today many types of
specialized fluids exist, which perform a diverse number of functions. The physical properties
and chemical constituents of these fluids are designed, monitored and altered to suit one or more
function at a time. These functions may be prioritized - either by design or when a solution to a
specific situation is required.

Drilling fluids usually contain a fluid phase and a solid phase. The fluid phase may consist of air,
oil or water or a combination of these. The solid phase may consist of formation material and
solid materials added to contribute to a certain function.


1.2 ROTARY DRILLING TECHNIQUE - INTRODUCTION TO DRILLING FLUIDS

The application of Science and Technology to boring holes through the earths crust is a dynamic
process. Documentation suggests that rotary drilling rigs with circulating systems were being
used as early as the mid-nineteenth century.
1
Since then, improving the economics of petroleum
production has been a driving force behind the advancement of drilling technology. More
recently, concerns regarding the safety of personnel and the protection of the environment have
played an equal role in this technology.

Today, the process of rotary drilling still has some similarities to the methods used over a century
ago. A cutting head or bit is attached to a series of connected hollow pipes. The outside
diameter of the pipe is smaller than that of the bit. This configuration is suspended from a set of
traveling blocks such that it can be run partly in compression and partly in tension. The part in
compression (the lower part) supplies the force on the bit. The bit is rotated clockwise as viewed
from above. Drilling fluid is pumped down the inside of the pipe and through the bit. As the bit
cuts through the rock, the cuttings are flushed away by the drilling fluid. The fluid continues to
transport the cuttings to the surface through the annular space between the pipe and the wall of
the hole. At the surface, the cuttings are separated and discarded. The Drilling Fluid is cleaned,
and treated with chemicals before being pumped down the pipe again. The general arrangement
of a drilling rig, mud pits, drill pipe, bit and casing is shown in Figure 1.1.



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Figure 1.1. Circulating System cross section

1 Pump 10 Cased Annulus
2 Shock Hose / Standpipe 11 Guide Base
3 Swivel / Top Drive 12 Blow Out Prevention Stack
4 Kelly / Drillpipe 13 Riser
5 Bottom Hole Assembly 14 Flowline
6 Bit 15 Diverter
7 Open hole annulus 16 Diverter Line
8 Casing Shoe 17 Shaker
9 Casing 18 Mud Pits
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A drilling operation can usually be divided into three distinct parts. The first involves drilling to
the targeted depth or pay-zone. This is done in a series of intervals of decreasing diameter.
The objective is to complete this part as quickly as possible, therefore the Drilling Fluid is
designed to aid to this end. Steel casing is lowered and cemented into place at the end of each
interval. While waiting for the cement to set, the physical or chemical properties of the Drilling
Fluid may be adjusted to suit the conditions and demands presented by the next sequence of
formations to be penetrated.

The second part of the drilling operation begins once the potential pay zone is reached. Here the
objective changes. It becomes essential to minimize formation damage caused by
contaminated Drilling Fluids. Specialized drill-in fluids may be used to aid in hydrocarbon
detection or to protect potential production zones.

The final stage occurs when the well is completed. The casing and cement are perforated.
The hydrostatic forces exerted on the formation are reduced enough to allow the fluids in the
formation to flow to surface, or a pump is installed or steam is injected etc. The fluids used in this
stage can have a significant influence on the productivity of the formation. Many operators are
using various types of completion fluids regularly.

As exploration and production costs increase, greater emphasis is placed on the role of drilling
and completion fluids. The Petroleum Industry recognizes that both the design and management
of Drilling Fluid systems play an important role in the success of a drilling operation. This is the
case in terms of reduced drilling time and in increased productivity. Thus, Drilling Fluid
technology continues to be a dynamic and multi-disciplinary science.


1.3 PRINCIPLE FUNCTIONS OF DRILLING FLUIDS

Drilling Fluid was probably first used to aid in the transport of drilled cuttings to the surface.
2
As
the drilling industry evolved, additional functions became both apparent and necessary. Today,
Drilling Fluid serves several principle functions.

The chemical and physical properties of any Drilling Fluid depend on its components. The
composition of a fluid may be altered or designed, in order to improve the efficiency of a
certain function. When this is done it is likely that other properties or functions will also be
affected. The efficiency of some functions can be affected by more than one property. An
example of this is the influence of both density and viscosity on the rate of penetration.

The functions of Drilling Fluids do have a practical order of importance. It is generally accepted
that the transport of cuttings and the control of sub-surface pressures are essential functions.
Other functions may take precedent at certain stages of the drilling program. Minor or inherent
functions are listed in section 1.3.11.


1.3.1 Improve Cuttings Removal Rates

As drilling proceeds, a great deal of emphasis is placed on the Drilling Fluids ability to remove
the drilled cuttings. The term hole cleaning is used frequently and the cuttings returning to
surface are observed continuously. Any changes in the size, shape, consistency, or the net
volume of cuttings are noted. If the material returning to surface contains cavings or
sloughings, adjustments to fluid properties are considered.

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The cuttings must be removed as quickly as possible to prevent annular blockage. This can
become more complicated in deviated wells where the cuttings tend to form a cuttings bed on
the low side of the hole. Further, the cuttings generated in some formations tend to be reactive in
water-based solutions. They may chemically degrade or disperse as a function of time. Usually
mechanical degradation occurs also. Cuttings may degrade to beyond the point of capture by the
solids removal equipment on surface, contributing to rheological or density-associated problems.

Several properties and parameters influence cuttings removal rates. The primary ones are the
viscosity and velocity of the transporting fluid. The viscosity may be expressed in terms of
funnel viscosity, yield point, consistency index, plastic viscosity, apparent viscosity, effective
viscosity and annular viscosity - depending on the specific application and the mathematical
model used. An accurate prediction of a fluids ability to transport cuttings can be quite
complicated, since most Drilling Fluids are non-Newtonian or shear thinning. In non-Newtonian
fluids, the effective viscosity decreases as the shear rate (velocity in this case) is increased. By
using mathematical models for a given fluid, its behavior under various dynamic conditions may
be predicted. Thus the correct combination of velocity and viscosity may be applied.

Other parameters affect the cuttings removal rate. These include the density of both the fluid and
the cuttings, and the size and shape of the cuttings. The mathematical modeling of fluid behavior
and the mechanisms of cuttings transport are discussed in detail in the section on Rheology.


1.3.2 Control Sub-surface Pressures

The prediction, detection and control of sub-surface pressures are an integral part of any drilling
operation. Safety and environmental concerns are the main motives for devoting attention to sub-
surface pressures.

As depth increases, the weight of the overlaying rock exerts increased pressure on the formation
being penetrated. Usually the pore size in the rocks is reduced. The bulk or net density of the
formation increases and any liquid or gas trapped in the rocks is subjected to increasing
pressure. The pressure profile of a well (pore pressure vs. depth) can be predicted through
seismic or extrapolated from offset well data. Unfortunately, pressure prediction is not always
accurate and pressure profiles are seldom linear. For the sake of simplicity, pressures may be
reported as the equivalent fluid density required to balance the formation pressure. The
pressure profile of a well or an interval may also be expressed in terms of its relationship to a
column of fresh water of equal height. That is; over, under, or normally pressured. Two
mechanisms may contribute to problems associated with drilling with an underbalanced fluid
column.
The first is related to stress relief and may result in borehole collapse. In tertiary or plastic
formations the symptoms are evident as squeezing. Often the remedy is mechanical - wiping the
hole. At times it is necessary to revert to increasing the fluid density to contain squeezing.

The second is related to the pressure exerted on the connate fluids. If the pressure exerted by
the Drilling Fluid doesn't exceed the pore pressure, formation fluids will flow into the well bore.
The results of an uncontrolled, flowing well can be disastrous. In competent formations, over
pressured shales may enter the wellbore at an excessive rate. Increased flowline gas levels may
accompany this phenomenon. In this case the usual remedy is also to increase the fluids
density.

Both the value of the density and the fluid constituents contributing to that value are monitored
closely during drilling operations. Several problems may result if the density is too high (over-
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balanced). These include borehole fracturing, slower penetration rates and rheological
problems caused by the build-up and size degradation of the fluids solid phase.

Rheological properties are also important when considering the effective density of the fluid
column. Changing the viscosity can alter the equivalent circulating density and increase the
surge / swab effect when reciprocating pipe. The effect of fluid density on various drilling
parameters is discussed during Rheology, Hole Stability and Problem Solving.


1.3.3 Suspend and Release Solids

Since most Drilling Fluids consist of materials in suspension as well as in solution, it is imperative
that particles composing the solid phase remain suspended. If particle settling is adverse, the
result can be costly. Problems such as barite settling on packers, or fill and bridges after trips or
while logging take time to correct. When circulation is stopped, certain constituents of the fluid
should form a greater degree of structure and gelation should occur. The degree to which this
happens is a function of time and is defined as the thixotropic properties of the fluid - indicated
by the fluids gel strengths. Thixotropic properties should be controlled. They shouldn't be so
excessive that circulation cant be resumed easily. They should be reversible such that after
shearing for a reasonable time, the fluid returns to its original viscosity. This is necessary
because at surface the fluid must have the ability to release the cuttings and high viscosity
impairs the efficiency of the solids removal equipment. Thixotropic properties of Drilling Fluids
are discussed in the chapters on Clay Chemistry and Rheology.


1.3.4 Maintain Borehole Stability

Problems involving the stability of the borehole always require time and expense to correct.
Occasionally a drilling operation fails when the problem can't be rectified in a timely manner. The
cause or combinations of causes to this problem vary and the solutions are diverse. Drilling
successfully through a problem formation may be entirely dependant on the Drilling Fluids
formulation, maintenance and modification.

Contributing factors to borehole instability include easily erodible formations such as evaporates
or permafrost. Or, the formation might be fractured - with a weak matrix - unable to withstand
overburden stresses. Many shales are hydratable and / or swelling, with a tendency to slough
after a certain time of exposure to drilling fluid. Effects of over pressured shales are sometimes
extremely difficult to correct and they may contain dangerous levels of gas. Overburden or
tectonic forces may cause wells to squeeze making it difficult to pull pipe, log or run casing.

There are several Drilling Fluid properties that can contribute to the maintenance of borehole
stability. The treatment and mechanisms vary depending on the cause or the potential cause.
An adjustment to the viscosity might alter the annular flow regime enough to prevent erosion.
Raising the specific gravity may be the only requirement for successful drilling through over
pressured zones. A wide range of inhibitive fluids has been developed. In some, the ionic
content of the liquid phase has been altered with various salts. The effects of these fluids may
be beneficiated with encapsulating polymers. In many areas, operators have found that drilling
with oil-based fluids has proven to be by far the best solution to borehole stability problems.

Drilling Fluid testing procedures and reporting formats are designed to monitor the particular
properties and parameters that contribute to the maintenance of borehole stability. This volume
contains a chapter on Borehole Stability.

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1.3.5 Protect Producing Formations

As production costs rise, increasing emphasis is placed on protecting producing formations from
potential damage caused by contact with borehole fluids. This protection can at times, be a
primary function of the fluid. Specialized drill-in, completion, and work over fluids are
designed and used in specific and localized applications.

Usually formation damage is attributed to the reduction in size, or the plugging of the rocks
natural porosity. Generally the mechanisms that cause damage may be classified into two
groups: Plugging associated with solids (including precipitates) and plugging associated with
fluid filtrate.
3


Fluid properties that may influence the success of a non-damaging fluid application include,
density, solids content, fluid loss and filtrate characteristics, viscosity, and the fluids ability to limit
corrosion. The background, theory and design parameters of non-damaging fluids are discussed
later in the manual.


1.3.6 Control Corrosion Rates

All metal components including drilling tools, casing and rig components must perform in a
corrosive environment. The results of excessive corrosion include casing failure, damage to
surface equipment and failure of down hole production tools.

Corrosion mechanisms encountered in drilling operations are usually related to dissolved
oxygen, carbon dioxide or hydrogen sulfide. Occasionally all three may be present. Usually
the fluid is maintained in an alkaline state to help impede corrosion rates. A broad range of
chemical additives is available to combat specific corrosion related problems. Corrosion is
discussed later in the course.


1.3.7 Seal the Wall of the Borehole

Drilling Fluids usually have a specific gravity sufficient to offset or counter-balance formation
pressures. This aids in supporting the rock and preventing formation fluids from entering the
wellbore. When the fluid column is overbalanced usually some fluid is lost to the formation.
The degree of loss depends on the pressure differential, the size of the pores in the rock and the
size and type of particles or bridging agents in the fluid.

If fluid is lost to the formation, several adverse affects may result. Whole fluid losses can be
expensive - especially in the case of oil-based fluids. Kick detection becomes hampered if
losses are continual while drilling. When the liquid phase or filtrate of the fluid is lost to the
formation, the solid phase becomes deposited as a cake on the wall of the hole. This cake may
be of sufficient consistency to cause the pipe to become stuck. Filtrate invasion may also affect
other Drilling Fluid functions, including the influence of the fluid on borehole stability or the
protection of producing formations.

The main methods of gauging the filtration characteristics of a Drilling Fluid include conducting
API filtration or high temperature / high-pressure filtration tests on the fluid. Other more involved
tests may be employed if required. The results of these tests are reported in volume of filtrate per
time unit, and cake thickness. The actual characteristics of the cake may be vitally important in
problem formations.
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Many different materials are available to effectively seal the wall of the borehole. They range in
sized from colloidal clays to golf-ball and larger sized materials. Their application depends on the
severity of the problem, and type of Drilling Fluid used. Fluid Loss Control is studied in detail in a
chapter of this volume.


1.3.8 Aid in Maximizing Penetration Rates

For years, substantial research has been directed at maximizing the Rate of Penetration (ROP)
while drilling. Several factors, including bit design, Bottom Hole Assembly design, bit hydraulics,
force on the bit, RPM, and Drilling Fluid properties have all proven to affect the ROP. The
justification for the research is mainly economical. Drilling time is reduced and interval lengths
can be increased.

Numerous studies have been conducted and models examined in an attempt to correlate Drilling
Fluid properties with changes to penetration rates. The fluids spurt loss
4
, certain filtration
characteristics
5
, solids characteristics and density all have an effect on the ROP. Several Drilling
Fluid properties are involved in a graphical model, called chip hold-down pressure. It attempts to
correlate the pressure differential between the Drilling Fluid column and the formation pore
pressure with drilling rates. Certain fluid properties are also considered when optimizing the
Hydraulic Horsepower at the bit. The effect of various fluid properties on penetration rates is
discussed throughout this volume.


1.3.9 Aid in the Retrieval and Interpretation of Formation Data

Many methods for evaluating production potential exist. Some are conducted while drilling, while
others are carried out when an interval is complete. The proper adjustment and maintenance of
Drilling Fluid properties may aid most evaluation techniques. The rheological properties are
important in terms of cuttings transport if accurate analysis of formation tops is to be made. The
particle size distribution of various solid phase components should also be considered when
running telemetry equipment or while coring. The thixotropic properties should be controlled -
both to allow for accurate flowline gas detection and to prevent solids settling while testing or
logging. The fluids ionic content may be adjusted to aid electric logging results. Tracer
elements may be incorporated into the fluid to aid in evaluation of recovered formation fluids after
drill stem testing. The minimization of formation damage caused by fluids remains the area of
greatest concern when considering the topic of retrieval and interpretation of formation data. This
function is an important part of Drilling Fluids design.


1.3.10 Cool and Lubricate the Bit and Drill String

While drilling ahead, a considerable amount of heat is generated by the frictional forces of the
rotating bit and drill string. This heat cannot be totally absorbed by the formation and must be
conducted away by the drilling fluid. A quantity of heat is then lost at the surface.

Lubrication is to a limited extent provided by the liquid phase and solids deposited on the wall as
a filter cake. However, when drilling conditions become adverse, operators rely on improved
Drilling Fluids formulation to aid in extending their engineering parameters. Wells are becoming
deeper, hotter and more deviated - sometimes horizontal or "S" shaped. The Drilling Fluid should
have the ability to minimize the influence of rotary torque and hole drag on well design. Various
friction-reducing Drilling Fluid additives have been developed and several methods are
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available to test their effectiveness on given fluids. Rotary torque and hole drag are discussed in
greater detail in the chapter on Problem Solving with Drilling Fluids.
1.3.11 Other Functions

There are several other functions or roles which Drilling Fluids may serve. Although they are
considered in drilling program design, fluid properties are not usually altered to enhance them.
They include; contributing to drill string buoyancy, driving downhole motors and telemetry
equipment, and the transport of data such as MWD and pore pressure data to surface.

Areas which are not functions but extremely important considerations, include the impact of a
particular Drilling Fluid system or its components on the safety and protection of personnel and
the environment. In most areas of the world these considerations take precedent over the benefit
of any other functions of Drilling Fluids.


1.4 COMPOSITION OF DRILLING FLUIDS

Drilling Fluids usually consists of two components; the fluid phase and the solid phase.

The fluid phase may consist of either a single fluid, or two immiscible fluids (an emulsion or
foam). If two fluids are used they are usually formulated to contain a discontinuous or dispersed
phase within a continuous phase. A general classification of Drilling Fluids based on their fluid
phase is outlined in table 1.1.


TABLE 1.1 CLASSIFICATION OF DRILLING FLUIDS SYSTEMS BASED ON THEIR FLUID
PHASE
Fluid Phase
Gas Water Oil

Gas

Foam

Water
Direct
Emulsion

Oil
Invert
Emulsion
Air or gas
alone
Air or gas
with water
and/or oil to
form foam
Oil free
water/brine
fluids
Continuous
water/brine
phase with
emulsified oil
Water free oil
fluid
Continuous oil
phase with
emulsified
water/brine


Various materials (solutes) may be dissolved in the fluid phase to change or control certain
properties of the fluid. A general classification of Drilling Fluids solutes is given in table 1.2.


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TABLE 1.2 DRILLING FLUIDS SOLUTES
a


Solute

Function

Solute

Function

Salts/Ionic Compounds

Increase density
(completion brines)
Aid inhibition
Prevent solution of
evaporites
Used as tracers
Adjust water activity

Polymers

Control fluid
loss
Deflocculation
Flocculation
Encapsulation
Control
viscosity
Alkaline Compounds Inhibit corrosion
Solubilize polymers
Alter charges on clays
Aid inhibition
Surfactants Corrosion
control
Emulsion
stabilization
Prevent bit
balling
Acids Cement contamination
treatment
Clay dispersion
Asphaltic derivatives Control fluid
loss
Suspension
properties
a) Note that not all substances are soluble in both oil and water

The benefit of gas-based fluid systems is realized in rapid penetration rates. Its application is
limited to competent, low-pressured formations. As formations become wet, mist, foam or stable
foam must be used.

Water is the most commonly used continuous phase due to its low cost and availability. Because
water is a polar medium it has the advantage of being able to dissolve many different substances.
This feature may also contribute to undesirable effects. Water dissolves gases, which cause
corrosion. The ionic compounds, which make up evaporate formations, are easily dissolved by
water - sometimes resulting in severe hole erosion. Most formation clays have an affinity for
water. The expansion forces generated when they adsorb water are often strong enough to
contribute to borehole instability.

To overcome these effects, various solutes may be incorporated into the water phase. These
have led to a general classification and nomenclature of water-based fluids systems, many of
which have been designed with some form of inhibition in mind. Water-Based Fluids and their
components are discussed later in this course.

Oil-based fluids have been commercially available since the 1940's. The disadvantages
inherent in water-based fluids may be overcome when oil becomes the continuous phase. This is
due to the non-polar nature of oil. It will not solubilize salts or react with clays. Most oil-based
fluids are an emulsion, with brine making up the dispersed phase. Oil-based fluids may be
formulated with diesel oil, or a more environmentally compatible low toxicity oil. Oil-based fluids
and their components are presented following the chapter on Water-Based Fluids.

The solid phase of Drilling Fluids consist of particles held in suspension by the liquid phase.
There are several ways of classifying solids in Drilling Fluids:

1. By size; colloidal to gravel sized.
2. By surface charge; reactive or inert.
3. By how they entered the fluid; drilled solids or "commercial solids".
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4. By their specific gravity; high or low gravity solids.

Drilled solids are derived from the formation. Although the presence of drilled solids may
improve filtration, viscosity or density characteristics, other additives perform these functions
more efficiently. Drilled solids are usually low gravity solids. Excessive concentrations of drilled
solids are undesirable (contaminants) as they contribute to abrasiveness and make rheological
properties difficult to control. The degree of tolerance a fluids system has for drilled solids
depends on the concentration of "commercial solids" and the availability of deflocculants within
the system. Commercial solids are non-soluble materials that are added purposely to a fluid
system to control a property. They may be broadly classified into five different functional groups
as outlined in table 1.3. The impact of the solid phase of Drilling Fluids is discussed throughout
both volumes of this manual.

TABLE 1.3 FUNCTIONS OF SOLID PHASE ADDITIVES

GROUP


FUNCTION

EXAMPLES
a


Weighting agents

Increase specific gravity

Barite, Hematite

Clays Increased viscosity, aid in
bridging, increase lubricity
Montmorillonite, Sepiolite


Bridging agents Seal porosity Fiber, Flakes, Resins,
Salts

Solid phase torque reducers Reduce rotary torque & hole drag Graphite, Teflon beads,
Bentonite

Hole stabilization additives Plug microfractures Asphalts, Gilsonite

a
Note: The examples given do not constitute a complete list.


1.5 PROPERTIES OF DRILLING FLUIDS

The properties of Drilling Fluids may be divided into two groups: physical properties and
chemical properties. The physical properties of a Drilling Fluid are usually influenced to some
degree by both the liquid and solid phases of the fluid. The chemical properties, which are
considered important, are influenced by constituent solutes including ionic species, polymers and
other dissolved compounds.

Various physical and chemical properties are incorporated into fluid design, monitored and
reported - especially when they pertain to a specific application or problem. These applications
include formation damage, high pressures, hole stability, high temperatures, contaminating
formations and friction.

Generally the properties applicable to the majority of fluids systems include specific gravity and
viscosity characteristics. Properties particular to specific fluids are outlined in Volume II of this
manual. The procedures for testing these properties are also outlined in Volume II.


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1.6 DUTIES AND RESPONSIBLITIES OF A MUD ENGINEER

The purpose of this section is to discuss the various aspects of the day-to-day activities of an Ava
Drilling Fluids Mud Engineer. As a representative of Ava, the most important skill you must
possess is the ability to communicate with all the stakeholders (e.g. Office operations, technical
service, sales; truckers; rig supervisors; crews).

An open discussion of the points below will give you an idea of the issues a Mud Engineer from
Ava S.p.A. will deal with on a daily basis.

1. Safety

Driving

Night driving
Hours on the road
Conditions
Defensive driving

On the rig

Mud tanks
Product stockpile/warehouse
PPE
Safety Certification(s)
Duties

Testing equipment

HTHP
Chemicals
Pipettes
Laboratory
Samples/shipping

Warehouse/Products

MSDS
ADR
Product Data Sheets

Cellular phone

Hands Free
Timing/Duration

2. Communication

Cellular phone

Hands Free
Timing/Duration

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Weekly Reports

Monday/Thursday

Problems

ASAP with information!

Truckers

Loads/timing
Road Conditions
Directions
Special Instructions

Engineer/Drilling Foreman/Toolpush

Mud Program
Drilling Program
Troubleshooting
Special Operations
Loads/timing

Derrickman/Rig Crew

Current mud properties/operations
Obstacles/Questions/Concerns
Mud Program Implementation
Drilling Program pre-planning
Troubleshooting
Special Operations cementing, logging, coring, running casing
Loads/timing OBM/WBM/Special additives
Mixing Instructions verbal/written
MSDS
ADR

3. Communication

Technical Services/Sales

Current mud properties/operations
Obstacles/Questions/Concerns
Mud Program Implementation
Drilling Program pre-planning
Troubleshooting Vital link to Ava customers
Samples product/mud/solids
Special Operations cementing, logging, coring, running casing
Loads/timing OBM/WBM/Special additives

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4. Logistics

Programmed products

Rig suitability
Availability
Quantities
Customer expectations

Warehouse inventory

Availability
Quantities
Ordering
Timing warehouse/rig
Pre-planning

Substitutions

Weights/clays
Polymers PHPAs, Xanthan, FLC, other
LCM
Lubricants
Defoamers

Crisis management

Lost circulation
Pressure control
Critical Sour operations

5. Reporting

Mud reports

Copies
Floppy disk(s)/downloads
Required Information

Summaries

Timing
Contents

AVA Software

Practice
Ask
Suggest

Telephone

Timing/timeliness/duration
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Timing/Frequency

Crisis communications

ASAP with information
Customer expectations
Ava Operations/sales expectations

6. Testing

Per instructions in Ava Mud Manual or as defined by various API
Bulletins
Timing/timeliness/frequency
Location
Samples
Pilot testing/laboratory analysis

7. Discussion

Safety

Personal
Rig
Fatigue

Driving

Moving violations
Tickets
Other

Hot Shots/Deliveries

Insurance
ADR

Duties

Organization - planning/Notes - records
Rig
Hauling

Service

Define/discuss
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References

1 H.C.H. Darley & George R. Gray, Composition and Properties of Drilling and Completion
Fluids, 5th ed. (Houston: Gulf Publishing Company, 1988), 38 ; all subsequent citations
are to this edition.

2 Darley and Gray, Composition and Properties, 38.

3 Thomas O. Allen and Allan P. Roberts, Production Operations, 3rd ed. (Tulsa: Oil and
Gas Consultants International, 1989), 2: 68, 69; All subsequent citations are to this
edition.

4 Darley & Gray, Composition and Properties, 416.

5 Darley & Gray, Composition and Properties, 422.


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CHAPTER 2

BASIC CHEMISTRY

2.1 KEY POINTS AND SUMMARY

2.2 BASIC DEFINITIONS
2.2.1 The Fundamental Units of Substances
2.2.2 Quantifying these Units
2.2.3 Chemical Formulas and Equations

2.3 CHEMICAL BONDING
2.3.1 Electron Shells, Ions and Valency
2.3.2 Ionic Bonding
2.3.3 Covalent and Mixed Bonding
2.3.4 Other Atomic Influences

2.4 SOLUTIONS
2.4.1 Types of Solutions
2.4.2 The Hydration of Ions
2.4.3 Water Solubility
2.4.4 Oil Solubility
2.4.5 Dispersions and Dispersability
2.4.6 Colloidal Systems and Suspensions
2.4.7 Equilibrium and Precipitation
2.4.8 Drilling Fluids: Multi-phase Homogenates

2.5 CHEMICAL CALCULATIONS
2.5.1 Molarity and Normality
2.5.2 Concentrations in Solutions and Suspensions
2.5.3 Converting and Calculating

2.6 ACIDS AND BASES
2.6.1 pH
2.6.2 Ionization Constant
2.6.3 Acids and Bases
2.6.4 Practical pH
2.6.5 Alkaline Drilling Mud's

2.7 SURFACE CHEMISTRY
2.7.1 Surfaces
2.7.2 Surface Tension
2.7.3 Emulsion and Foam
2.7.4 Surface Charges
2.7.5 Other Surface Phenomena
2.7.6 Semi permeable Membranes and Osmotic Pressure
2.7.7 Altering Surface Chemistry
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2.1 KEY POINTS AND SUMMARY

Ava Drilling Fluids has included this chapter to serve as an introduction to petroleum and mud
chemistry, and should be used as a review, or as a quick reference. As with any science it would
be impossible to include every facet of chemistry within this short introduction. Therefore, for the
sake of succinctness, mainly the concepts and terms that apply to drilling fluids are addressed
here. Some concepts are expanded upon later in the manual, as required for a better
understanding of specific chemical phenomena.

It is recommended that any reader who has an additional interest in basic chemistry, turn to a first
year text book such as Chem One by Waser, Trueblood and Knobles, published by McGraw-Hill.


2.2 BASIC DEFINITIONS

2.2.1 Fundamental Units of Substances

If you put a cube of sugar in your hand it will have a specific amount of weight associated with it,
or in scientific terms, the cube of sugar has a specific mass (for argument sake its weight or
mass = 1 gram). The term mass refers to the quantity of matter contained in a particle or body.
On the other hand, the term matter refers to anything that has mass or occupies space. The
constituents and the behavior of matter are of concern and interest to scientists and lay-people
alike.

Matter exists in three generally accepted states solids, liquids and gases. There are several ways
to classify matter. One simple method is to group matter by particle size as outlined in Table 2.1.

Table 2.1
Name Example Size Visibility
Sub Atomic Protons, Neutrons,
Electrons
<<1x10
-12
meters Inference by high
speed bombardment
Atoms Elements <1x10
-9
meters X-rays
Molecules Groups of atoms <1x10
-8
meters Electron microscopes
Compounds/materials Groups of molecules 1x10
-8
meters to
visible
Microscopes to the
human eye

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Fig 1 & 2 are both high powered microscopic pictures of some common materials, notice the
ordered structure of the Plexiglas compared to the random order of the emulsion.


Fig. 1. A picture of Plexiglas. Each particle is 2x10
-6
meters in length.


Fig. 2. A picture of oil in water or an emulsion.


In the 19
th
& 20
th
Century, scientists have come to understand what constitutes the basic building
blocks of matter. Today, some of the smallest particles known are quarks, anti-quarks and
gluons. Combinations of these particles give rise to mesons, baryons, and combinations of these
particles give rise to neutrons, protons, and electrons and before you know it you have a cube of
sugar in your hand.

For interest sake, Quarks, discovered in 1969, exist in at least six different flavors: up, down,
strange, charm, top and bottom. Each flavor comes in three colors, red, green and blue
1
.
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Protons, Electrons and Neutrons

At a sub-atomic level matter is made up of three particles, protons, electrons and neutrons. If you
picture an atom as a small sphere, the core of that sphere is made up of neutrons (n, neutral,
atomic mass unit (AMU) = 1.009), protons (p, positive charge, AMU = 1.0) and orbiting that core
(like satellites) are electrons (e, negative charge, AMU = 0.0005). An atom with a specific number
of protons is classified as an element. The element carbon (C) has six protons, six electrons and
6 neutrons for an atomic weight of 12.011.

An atom has equal numbers of protons and electrons (net charge = 0), but can vary in the
number of neutrons present in the core. Elements that have extra neutrons but the same number
of protons are called isotopes. Isotopes have similar chemical properties but differ in mass.
Carbon-14 (
14
C, AMU = 14, used in archeology to carbon date artifacts) is an isotope of carbon
with two additional neutrons. Carbon has 7 different isotopes.

Neutrons and protons are held together by nuclear forces. Of interest is the removal or addition
of electrons to an atom. By adding an electron (-1) to an atom, we would have a negative (1)
charge, i.e. a negative ion (anion). If we took an electron away, the atom would have a net
positive (+1) charge, i.e. a positive ion (cation). This is important, as this is the foundation to
understanding the interactions between clays, rocks and mud systems.

There are currently 111 known elements. It is believed that all of the matter in the universe is
composed of these elements. Theoretical physicists believe that the lightest elements were
formed in less than half an hour, from a primordial mixture of neutrons and electromagnetic
radiation.

Table 2.2 lists the known elements in an order that groups elements of like properties together
and it is called the Periodic Table of the Elements.

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Table 2.2: Periodic table of the Elements (Mendeleev)



Alkaline metals: Group I (1A)
Alkaline earth metals: Group II (2A)
Transition metals: Groups 3B, 4B, 5B, 6B, 7B, 8, 1B, 2B
Non metals: Groups III, IV, V, VI, VII (3A, 4A, 5A, 6A, 7A)
Halogens: Group VII (7A)
Noble gas: Group VIII (8A)
Lanthanides: From Cerium to Lutetium
Actinides: From Thorium to Lawrencium
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Chemicals

Two or more elements may combine chemically to form a molecule (or compound). A molecule
can be as simple as two hydrogen atoms H
2
(hydrogen gas, fig. 3) or as complex as C
10
H
14
N
2

(nicotine, fig. 4). A molecule consists of differing atoms (elements) arranged in a specific order
and are represented by a chemical formula. Chemical formulas can be visualized by drawing out
chemical structures based on the known geometry of the atoms and how they interact with each
other. With 111 elements, the possible numbers of molecules are limitless.


H H
N
N
CH
3
Fig 3. Hydrogen gas
Fig 4. Nicotine



Bonds hold atoms together; these bonds are complex interactions between the protons and
electrons of both atoms. To make a bond between two atoms you must add energy to the two
atoms, force them close together and a bond will form. A bond between two atoms contains a lot
of energy, although orders of magnitude lower than the energy holding an atom together. Think
about the difference between breaking a chemical bond (TNT explosion) and an atom (an atom
bomb explosion)!

Most reactions are reversible so if you add enough energy you will be able to break the bond
between the two elements, which will release the energy stored in the bond (usually released as
heat). If more energy is required to break a bond than is released by the bond the reaction is
called endothermic i.e. a thermal cracker adds energy to break apart hydrocarbons. If more
energy is released when the bond breaks than is required to break the bond then the reaction is
called exothermic i.e. conventional explosives.

An exothermic reaction can also be as simple as dissolving a bag of caustic soda in water. The
heat required to break apart the ionic lattice (lattice energy) is less than the energy given off as
water rushes to hydrate the ions (hydration energy); therefore caustic or caustic potash will give
off large amounts of energy in the form of heat when dissolved in water. Salt on the other hand is
endothermic when dissolved in water i.e. the lattice energy is greater than the hydration energy.
See fig. 5.
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Figure 5



Energy comes in many different forms, chemical reactions (stored energy), heat, light, sound or
an electric current. An example of a chemical reaction is the formation of water. A liquid formed
by the combination of two elements, hydrogen and oxygen (which are gasses) in the presence of
heat. Water can be reacted back into hydrogen and oxygen by adding energy in the form of an
electric current (electrolysis).

2H
2
O H
2
+ O
2
e
-1
Pt
H
2
+ O
2
Spark


All of the chemicals added to drilling fluids are molecules or chemical compounds; some of the
more common ones are listed in Table 2.3
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Table 2.3
Name Chemical formula Common Name
Aluminum sulfate Al
2
(SO
4
)
3

Barium sulfate BaSO
4
Barite
Calcium bromide CaBr
2

Calcium chloride CaCl
2

Calcium carbonate CaCO
3
Limestone
Calcium hydroxide Ca(OH)
2
Hydrated lime
Calcium oxide CaO Quick lime
Calcium sulfate CaSO
4
Anhydrite
Calcium sulfate bis-hydrate CaSO
4
2H
2
O Gypsum
Hydrochloric acid HCl
Potassium chloride KCl Potash
Potassium hydroxide KOH Caustic Potash
Sodium bicarbonate NaHCO
3
Bicarb
Sodium bromide NaBr
Sodium carbonate Na
2
CO
3
Soda ash
Sodium chloride NaCl Salt
Sulfuric acid H
2
SO
4

Zinc bromide ZnBr

Notice in this list of chemical compounds that they are all salts of some kind! This gives us an
important distinction. Compounds or molecules that have no carbon/hydrogen in them are
classified as inorganic compounds; a common example of an inorganic compound would be
table salt. Compounds that have a carbon/hydrogen atoms contained within the molecule are
classified as organic compounds of which oil would be a common example.

Molecules have very different properties from each other and when they group together they tend
to form into structures that are common to us; compare a sugar cube, a coffee cup and water.
Sugar molecules in large quantities stack together (like CDs stacked in a tower) in the form of a
crystal. Styrene Fig. 6 is chemically reacted together to give polystyrene (plastic cup), a
macromolecule.

Styrene
Int.
x
Polystyrene
Fig 6


Water molecules at room temperature are clustered together and randomly float around bumping
into each other. This gives us a property we recognize as liquid water. These three compounds
all have very different states from each other.

What if we bring the temperature of the water down to 20C, then what happens? The water
molecules slow down enough to stack together and crystallize to give ice. A structure similar to
the sugar cube. Almost all compounds have the three physical states associated with them
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(liquid, solid, gas), water is one which we all have experience with. Most other types of chemicals
require extreme conditions to change there phase from liquid to gas or solid. One of the ways to
make sodium metal and chlorine gas is to heat table salt past 430C to melt it. If you bring air
down to 177C then it would turn into a liquid.

Other common terms of solids classification a drilling engineer will use are crystals (above),
colloids and macromolecules. Colloids can be described as compounds that are held in a liquid
by their interaction with the surrounding fluid, a common colloid is blood. In drilling muds clays
are colloids. Drilling fluid polymers are macromolecules, and they consist of many thousands if
not millions of repeating molecules put together in a chain. Geologists define a mineral as a
naturally occurring, inorganic crystalline solid that has a definite chemical composition and
possesses characteristic physical properties. Molecules often combine in an ordered, repeating
structures to form crystals, the normal form of the solid state of matter. The arrangement of the
ions, atoms, or molecules in a crystal comprises a definite pattern called a lattice (see fig 5).


2.2.2 Quantifying these Units

Atoms and elements may be categorized by several different methods. The Periodic Table is
one way of classifying elements which most of us are familiar with. The chief function of the
periodic table is to serve as a fundamental framework for the systematic organization of
chemistry. Figure 7 depicts the key to a simple rendition of the periodic table shown in Table 2.2.
The top number 6 represents the atomic number of carbon, the C is the symbol of carbon and the
12.01 is the atomic weight.

Fig. 7



Other varieties of the periodic table provide a much more in-depth description of the
characteristics and properties of elements. The elements are sometimes classified as either
metals or non-metals. Metals are described as elements whose compounds form positive ions in
solution and whose oxides form hydroxides rather than acids with water.

The atomic number is simply the number of protons of each atom of an element. It is the main
identity parameter of each element. (Each element has a different number of protons and hence,
a different atomic number). Since atoms are electrically neutral, the atomic number is also the
same as the number of negatively charged electrons orbiting the nucleus of that atom.

The atomic weight of an element refers to the total mass of all the constituents of each of its
atoms, including protons, neutrons and electrons. The mass of one proton is equal to one atomic
mass unit (AMU). The mass of a neutron is 1.009 AMU and an electron is 0.000544 AMU. Since
the mass of an electron is so minute and the mass of a neutron is almost 1, one would think that
the atomic weight of an element would be a whole number. A look at Table 2.2 shows this is not
true. The reason is, that the atomic weight is an average of the weights of all of the isotopes or
species of atoms of an element.

The atoms of individual elements all have the same atomic number, equal to the number of
protons in the nucleus. In most cases each atoms nucleus has an equal number of neutrons. An
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isotope of an element is composed of atoms with one or more extra neutrons in their nuclei. This
gives the isotope a larger atomic weight, increasing the average atomic weight of the element;
hence the atomic weight can be a fraction.

Twenty-one elements have no isotopes, each consisting of only one kind of atom. The remaining
natural elements have from 2 to 10 isotopes each. The
12
C is the international standard of atomic
weight. Its nucleus has 6 protons and 6 neutrons. When 7 neutrons are present, its atomic weight
becomes 13 and the element is called carbon 13 with the abbreviation denoted by a superscript
(
13
C). Radioactive isotopes decay, emitting energy in the form of particles. Ultimately a new, more
stable element is formed. Tritium is a man-made radioactive isotope of hydrogen, used
occasionally in drilling fluids. Because it decays at a known rate (a 12.5 year life) and
concentrations are identified easily, it makes a good tracer.

The term molecular weight is used regularly in this manual. It is a chemical term, which simply
refers to the sum of the atomic weights of the atoms in a molecule. The molecular weight of the
common natural gas methane (CH
4
) is 16.043, the atomic weight being

C=12.011
4H=4x1.0079
H H
H
H
CH
4
16.04
16.031300
C 74.87% H 25.13%



2.2.3 Chemical Formulas & Equations

Several types of formulas serve to designate chemical compounds, each type conveying different
information. The empirical formula of a compound is the ratio of moles of each element present
in the compound, expressed in the form of small whole numbers. The empirical formula of any
compound can be expressed as small whole numbers because atoms are indivisible. If the ratio
of moles were 1Fe:1.5O, as it is in iron (III) oxide, the empirical formula would be written as
Fe
2
O
3
.

Structural formulas provide information on the detailed atomic arrangement in a compound. The
ensuing text shows structural formulas when explaining covalent bonding. The structural formula
for acetylene is...

C C H H or H H
fig 8


Chemical equations are used to show the reactions of substances in terms of their formulas,
relative numbers of reactants and the products involved. By definition chemical equations should
be balanced. They should show the same number of each atom on both sides and the net charge
should be the same on both sides. Balancing an equation can mean re-arranging it to fit this
definition. For example, an unbalanced equation:

C
3
H
8
O + O
2
CO
2
+ H
2
O
heat


The simplest procedure is to first balance an atomic species that appears in only one compound
on each side, starting with C.
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C
3
H
8
O + O
2
3CO
2
+ H
2
O
heat


H also appears in only one compound on each side. H can be balanced by putting 4H
2
O on the
right.

C
3
H
8
O + O
2
3CO
2
+ 4H
2
O
heat


Since there are now 10 oxygen atoms on the right there must be 10 on the left. There is already
one atom of O in each molecule of C
3
H
8
O, therefore:

C
3
H
8
O + 4.5O
2
3CO
2
+ 4H
2
O
heat


Fractional coefficients are acceptable.


2.3 CHEMICAL BONDING

The preceding text explained that a compound is a combination of two or more elements
combined chemically. A chemical bond is an attractive force between atoms, which is strong
enough to permit the combined aggregate to function as a unit. In simple terms, a bond is formed
when protons from the other atom are sharing electrons from the other atom. There are three
principal types of chemical bonds that are important. These include: ionic, covalent, and hydrogen
bonds.


Table 2.4 Summary of Chemical Bonds
Bond Type Length (nm) Strength (kcal/mole) in water
Covalent 0.15 90
Ionic 0.25 3
Hydrogen 0.30 1


2.3.1 Electron Shells, Ions and Valency (oxidation state)

A simplified method for understanding the way in which electron orbitals are arranged around an
atomic nucleus is to consider the valence-bond (VB) model. Electrons are arranged in shells (s,
p, d or f), orbits or electron clouds around the nucleus. Figure 9 shows an s orbital and the p
orbitals, the most important in forming ionic or covalent bonds. These figures represent the
theoretical pathways the electrons follow.

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s orbital
1p orbital
1 s orbital
& 1 p oribtal
2p orbitals 3p orbitals
fig 9


The closest or first shell, s has the lowest energy level and may contain a maximum of 2
electrons. The energy levels increase with the distance from the nucleus. The next orbital p may
contain a maximum of 6 electrons one in each lobe. Table 2.5 helps to explain the arrangement
of electrons in the first twenty elements.

Table 2.5
Electron orbitals in the first 20 elements
Number of electrons per orbital
Element Atomic number 1 s 2 s 2 p 3 s 3 p 4 s Valence electrons
Hydrogen 1 1 1
Helium 2 2 0
Lithium 3 2 1 1
Beryllium 4 2 2 2
Boron 5 2 2 1 3
Carbon 6 2 2 2 4
Nitrogen 7 2 2 3 5
Oxygen 8 2 2 4 6
Fluorine 9 2 2 5 7
Neon 10 2 2 6 0
Sodium 11 2 2 6 1 1
Magnesium 12 2 2 6 2 2
Aluminum 13 2 2 6 2 1 3
Silicon 14 2 2 6 2 2 4
Phosphorus 15 2 2 6 2 3 5
Sulfur 16 2 2 6 2 4 6
Chlorine 17 2 2 6 2 5 7
Argon 18 2 2 6 2 6 0
Potassium 19 2 2 6 2 6 1 1
Calcium 20 2 2 6 2 6 2 2

When electrons arrange themselves around a nucleus, the innermost shells are always filled first.
Electrons also have a tendency to try to keep the other shells of an atom full. Table 2.5 shows
that these shells are not always filled. Sodium (Na) for example, has 2 electrons in the first s
shell, 2 in the second s shell, 6 in the second p shell, but only 1 in the third s shell.


Islands of Stability

Three elements in table 2.4 have zero valence electrons, helium, neon, and argon. These
elements are called noble gases and are known to be the most inert elements in the universe.
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The reason for this inertness has to do with the electrons surrounding these elements. The
orbitals surrounding the noble gases are completely full. Hence the electronic charges of these
elements are entirely balanced and utterly un-reactive towards other electrons. With this
knowledge we can look at every other element and say in a generalized way that (octet rule) all
other elements will lose or gain only enough electrons to get that element to a noble state or
every element wants to be a noble element! In terms of electrons every element wants to fill the s
orbitals (2 electrons) and the p orbitals (6 electrons).

In simple terms we can look at sodium and say it wants to get to neon so it will lose one electron
and become a Na
+
cation. The energy required to remove that electron is called the ionization
potential (IP), fig 10. The IP for sodium = 118 Kcal/mole

Fig. 10
Na Na
+
+ e
-1
H
o
=IP

Elements in the first row are known to have low IPs and are known to be electropositive
elements. Elements to the far right of the periodic table (halogens) are known to be
electronegative. These elements have an electron affinity (EA) i.e. they love electrons because
it makes them have a noble type electronic structure fig 11. The EA for fluorine to go to a fluorine
anion = 78.3 Kcal/mole.

Fig. 11
F + e
-1
F
-1
H
o
=EA


Electropositive (alkali metals) and electronegative (halogen) elements tend to lose and gain
electrons so easily they form pairs of ions. This type of bonding is described as ionic bonding.

For compounds in the middle of the table the energy required to lose or gain enough electrons to
get to a noble state is high, for carbon to have an electronic state similar to He the IP = 1480
Kcal/mole!

Fig. 12
C C
4+
+ 4e
-1
H
o
=1480.7Kcal/mole


Consequently these elements get to their octet (2+6) state by sharing electrons. Bonds in which
two (or more) electrons are shared are described as covalent bonds.

Fig. 13
+ 4H C H
H
H C
H


Carbon thinks that it is neon and hydrogen thinks it is helium, and the molecule is very stable.

Elements that have the greatest electronegativity are in the far top right of the periodic table;
those with the weakest are in the lower left of the periodic table. This is important because when
you have two elements joined together by a covalent bond, the more electronegative atom will
concentrate more of the electron density to itself. This creates a dipole moment and can be used
to visualize where a charge potential resides on a molecule.
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Fig. 14
C F C O Al C B Cl
dipole moment
(+) (-)


These are not full +/- charges more like hints of charges (). But these hints can be powerful
enough to create viscosity in a drilling mud.

2.3.2 Ionic Bonding

An ionic bond results from the electrostatic attraction between oppositely charged ions. This bond
may be thought of as the transfer of an electron from one atom to another such that two
oppositely charged ions result. The energy of these bonds varies depending on where the
element is in the periodic table top right or bottom left. Thus it requires more energy to break an
ionic bond between two small ions (top of table). Ionic crystals are substances in which oppositely
charged ions are packed together in a highly regular three-dimensional array, held together
chiefly by ionic bonds. In sodium chloride crystals, equal numbers of Na
+
ions and Cl
-
ions occur
in an intermittent regular pattern. It is important to realize that sodium chloride crystals do not
contain actual NaCl molecules, but only Na
+
and Cl
-
ions. This applies also to molten sodium
chloride or an aqueous solution of sodium chloride. These properties are applicable to all ionic
compounds. The compounds listed in Table 2.3 are all ionic compounds.

Fig. 15
O
S
O
O
-1 -1
O


Sulfate (SO
4
-2
) (fig 15) is called a divalent anionic compound because it is a compound with a
net, double negative charge. Sodium (Na
+
) is a monovalent cation.


2.3.3 Covalent and Mixed Bonding

Lewis first proposed the idea that covalent bonds involved shared pairs of electrons in 1916.
However, it was not until the development of Quantum Mechanics (the theory developed from
Planks Quantum Principle and Heisenbergs Uncertainty Principle) that a clear understanding of
covalent bonding became possible. Because of its simplicity, the Lewis model is still commonly
used today. This section does not consider Quantum Mechanics.

Like ionic bonding, the effect of covalent bonding is to satisfy the atoms tendency to obtain a full
electron shell. A single bond involves the sharing of 2 electrons. Double and triple bonds share 4
and 6 electrons respectively. Bonds of intermediate multiplicity also exist. When a molecule is
depicted on paper using a structural formula, these bonds are described using single, double or
triple lines between atoms. Unshared outer electrons are sometimes represented by dots:
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Fig. 16

CH
3
CH
2
O
H
CH
2
CH CH
CH
2
C C H H
Ethanol Butadiene
Acetylene
H
2
N
NH
2
1,6-diamniohexane


When electron pairs are shared by two nuclei, the bonding electrons are relatively localized in the
region of the two nuclei. Frequently a degree of delocalization occurs when the shared electrons
have a choice of orbitals.

In a covalently bonded molecule, the center of the positive charge may not coincide with the
center of the negative charge (this depends on the electronegativity of the two atoms). When this
occurs, the molecule retains electric dipole moments. When the dipole moments are permanent,
the molecule is said to be polar. Water is a polar molecule. The end with the oxygen atom has an
overall net negative charge, while the end with the two hydrogen atoms has an overall net
positive charge. (The center of the positive charge is halfway between the two H atoms). The
effect is as though the oxygen was keeping the hydrogens electrons for longer than its fair share
of time. This electrical effect helps many ionic compounds such as salts; dissolve in covalent
compounds like water (see fig 5). Oil is an example of a non-polar liquid.

Fig. 17
H
O
H
2

+
O
H
Dipole in water
Electron orbitals in water


Covalent bonds provide strong attraction between the atoms comprising a molecule (see table
2.4). However, the forces between individual molecules are not necessarily as ridged in covalent
compounds as ionic compounds. Therefore covalent compounds usually retain less structure
than ionic compounds. That is, they tend to be liquids or gases at normal temperatures. In most
cases, covalent compounds with higher molecular weights have higher boiling points. The degree
of polarity of a compound can also influence its boiling point, since a greater attraction between
molecules impedes thermally induced random molecular motion. This is why the H
2
S is a gas,
even though it is heavier than H
2
O, a liquid.

Mixed-bonding is fairly common in nature. The term refers to a molecule whose components have
both ionic bonds and covalent bonds. CaCO
3
is an example; CO
3
is a covalent molecule ionically
bonded to a calcium 2 plus cation. Table 2.3 gives some examples.


2.3.4 Other Atomic Influences

Van der Waals forces and hydrogen bonds play an important role in both clay chemistry and
polymer chemistry.
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Weak attractive forces may exist between uncharged atoms or molecules even in the absence of
any tendency to form covalent bonds. Collectively these are known as Van der Waals forces. Van
der Waals forces are of very short range compared to the range of electrostatic forces between
ions. Van der Waals forces act as attractive forces between the unit layers in clay suspensions.
One example is the forces, which act between molecules with permanent dipoles - polar
molecules.

Another example is an attractive force called the Dispersion Force or London Force. This force
can act on atoms and molecules with no permanent dipoles or charge distribution. It results when
two atoms or molecules come close enough to deform the electronic charge distribution of the
given atom or molecule. This induces dipole moments in them.

A hydrogen bond is an attractive force or bridge occurring in polar compounds such as water.
Here, a hydrogen atom of one molecule is attracted to two unshared electrons of another. The
hydrogen atom is the positive end of one polar molecule. It forms a linkage with the electro
negative end of another such molecule. In the formula below, the hydrogen atom in the center is
the bridge.

Fig. 18


Hydrogen bonds are much weaker than covalent bonds, but they have a pronounced effect on
the properties in which they occur
2
. This pertains to melting points, boiling points and crystal
structure. Hydrogen bonding contributes to the viscosification characteristics of Xanthan gum and
the encapsulating characteristics of PHPA polymers.

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A metallic bond is found in metals: valence electrons of each atom are not bonded to atoms but
belongs to the overall metal; they function as glue that holds together all the atoms of the solid.


2.4 SOLUTIONS

2.4.1 Types of Solutions

A solution may be defined as a uniformly dispersed mixture at the molecular or ionic level.
(Sometimes a solution is incorrectly referred to as a homogeneous mixture, but in its strict sense
the term homogeneous refers to the chemical constitution of a compound or element.)

In a true solution one or more substances called solutes are uniformly dispersed in one or more
other substances called the solvent. Solutes may be present in water, usually in the form of
molecules (sugars) or ions (salts). Solutes may also be gaseous or liquid. When two liquids
exhibit mutual solvency they are said to be miscible. Solvents can either be polar or non-polar.
The most common solvent is water. It is highly, polar, whereas hydrocarbon solvents are non-
polar.

The proportion of substances in a solution depends on their limits of solubility. The solubility of
one substance in another is the maximum amount that can be dissolved at a given temperature
and pressure. A solution containing such a maximum amount of solute is said to be saturated. A
state of super-saturation can be created i.e. by heating water more sugar can be dissolved in the
water. Such solutions are unstable in practical use because if the temperature changes drastically
the solute may spontaneously precipitate or settle out as small, particulate solid compounds.
Supersaturated salt solutions are used as completion fluids with the salt particles acting as pore
plugging agents. Saturation is discussed again in the subsection, Water Solubility.

A solute, which imparts ionic conductivity when dissolved in water, is called an electrolyte. A
familiar example is sodium chloride. In the solid state it exists as an ionic compound. But when
dissolved in water, individual Cl
-
and Na
+
ions separate and the water becomes a better electric
conductor see Fig 5. Non-electrolytic substances usually dissolve as chargeless molecules. The
resultant solution does not efficiently conduct a current.


2.4.2 The Hydration of Ions

The term hydration refers to the solvation of ions in water. The strong affinity of water molecules
for dissociated ions causes them to acquire a film of highly bound water molecules as depicted in
Fig 5.

The density of the charge on the ion affects the strength of the bond. Some salts, especially those
with multi-valent ions such as calcium are called hydrous; they actually adsorb water from the
atmosphere. If the water is removed by heating, the crystals are called anhydrous. The size of
the ion also contributes to the strength of attachment of water molecules, increasing with
decreasing size.

Hydration increases the effective diameter of an ion. The exact number of water molecules
associated with any given ion is difficult to specify, especially if the number of free or available
H
2
O molecules are limited. Many uncharged molecules in aqueous solutions can be hydrogen
bonded to water molecules, for example NH
3
.

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2.4.3 Water Solubility

The solubility of molecules is a complex subject in which the principles of electrolytic dissociation,
diffusion and thermodynamics play controlling roles. For our purposes it is worthwhile to note the
following points.

An important generalization is that substances with similar intermolecular attractive forces tend to
be soluble in one another. Like dissolves like. That is, many non-polar substances are soluble in
non-polar solvents and many ionic compounds are soluble in polar solvents.

Because water is highly polar, it is an excellent solvent. Many ionic compounds are soluble in
water. The hydration energies of these compounds (their affinity for water) are greater than their
lattice energy (the strength of the bond holding the ion in place, within the crystal). Stated in
another way: a substance will dissolve in water if the forces of attraction between water
molecules and the ions (or ionic compounds) in the solid are greater than the forces of attraction
between oppositely charged ions in the crystal.

Table 2.7: Relative Water Solubilities of Some Common Compounds Containing Ionic Bonds

Water Solubility Cation Anion Compound Water Solubility Cation Anion Compound
Soluble Na
+
OH
-
NaOH Slightly Soluble Mg
2+
HCO
3
-
Mg(HCO
3
)
2

Na
+
Cl
-
NaCl Mg
2+
S
2-
MgS
Na
+
HCO
3
-
NaHCO
3
Ca
2+
OH
-
Ca(OH)
2

Na
+
CO
3
2-
Na
2
CO
3
Ca
2+
HCO
3
-
Ca(HCO
3
)
2

Na
+
SO
4
2-
Na
2
SO
4
Ca
2+
SO
4
2-
CaSO
4

Na
+
S
2-
Na
2
S Ca
2+
S
2-
CaS
K
+
OH
-
KOH Ba
2+
HCO
3
-
Ba(HCO
3
)
2

K
+
Cl
-
KCl
K
+
HCO
3
-
KHCO
3
Insoluble Mg
2+
OH
-
Mg(OH)
2

K
+
CO
3
2-
K
2
CO
3
Mg
2+
CO
3
2-
MgCO
3

K
+
SO
4
2-
K
2
SO
4
Ca
2+
CO
3
2-
CaCO
3

K
+
S
2-
K
2
S Ba
2+
CO
3
2-
BaCO
3

Mg
2+
Cl
-
MgCl
2
Ba
2+
SO
4
2-
BaSO
4

Mg
2+
SO
4
2-
MgSO
4
Zn
+2
S
-2
ZnS
Ca
2+
Cl
-
CaCl
2
Fe
+2
S
-2
FeS
Ba
2+
OH
-
Ba(OH)
2
Ag
+
Cl
-
AgCl
Ba
2+
Cl
-
BaCl
2

Ba
2+
S
2-
BaS
Al
3+
SO
4
2-
Al
2
(SO
4
)
3



Table 2.7 shows the relative water solubilities of several commonly used ionic compounds.
Usually, crystals composed of monovalent ions such as NaCl have the lowest lattice energy and
are the most soluble. Crystals that contain multi-valent ions such as BaSO
4
(Ba
2+
, SO
4
2-
) may not
be soluble in water at all. Their lattice energy is too high. Crystals such as CaCO
3
(Ca
2+
, CO
3
2-
)
although not soluble in water, can be dissolved in aqueous solutions having a higher degree of
polarity than water such as HCl. Sized CaCO
3
is employed as a pore-plugging solid phase in
some drill-in or completion fluids. The CaCO
3
is later solubilized with an acid wash, leaving open
porosity. Some lattice bonding energy may be lost as heat (exothermic) during solvation. This can
be seen in practice especially when mixing NaOH or CaCl
2
.

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Many covalent compounds are also able to solvate in water. They qualify under our definition of
solutes because they molecularly disperse in water. A degree of molecular polarity is necessary
for solvation to occur. Sugars, starches and alcohols are examples of polar, covalent compounds
that are water-soluble. Non-polar covalent compounds, including oils and asphalts are usually
insoluble in water.

When a solution is in contact with additional pure solute, further solvation depends on the
concentration of solute already in solution. A solution is said to be saturated when a state of
dynamic equilibrium exists between dissolved solute and any excess solid solute. That is, the
number of ions or molecules escaping from the crystal lattice into the solution is the same as
those leaving the solution to re-join the crystal lattice. Again, the concentration of solute in a
saturated solution is called its solubility (s). Two liquids may be mutually soluble in all
proportions, water and ethanol for example. For such solutions the term solubility is meaningless
since saturation is unattainable.

The solubility of most of the chemicals used in drilling fluids increases with temperature. This is
an important consideration when drilling evaporates such as the prairie evaporite with saturated
drilling fluids. In order to ensure formation dissolution does not occur, supersaturated solutions
are often used. Calculations and pilot testing should be made at bottom hole, static temperatures.
Fig 19 demonstrates the effect that temperature can have on two different compounds.

Solubility of chemicals is related to the following equilibrium reaction:

A + B AB K
s
= [A][B]

Where K
s
is a constant depending on temperature and is called solubility product. Solubility is
suppressed if other compounds with common ions are present in solution.

Example 1:
Calculate the solubility of AgCl, having K
s
= 10
-10
.

S = [Ag
+
] = [Cl
-
] =
s
K = 10
-5
M

Three cases are possible:
If [A][B] < K
s
: no precipitation of salt occurs
If [A][B] = K
s
: saturated solution
If [A][B] > K
s
: precipitation of salt occurs (AB)
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Fig. 19: KNO
3
black line, NaCl dotted line.

0
50
100
150
200
250
0 10 20 30 40 50 60 70 80 90 100
Temperature (oC)
S
o
l
u
b
i
l
i
t
y

g
/
1
0
0
g

W
a
t
e
r


A further consideration is that the presence of other ionic or molecular species in a given solution
will suppress the solubility of the chemicals or salts to be added. Generally when two salts are
present in solution the most soluble one suppresses the solubility of the other one.

Water-based drilling fluids are good solvents for most gases. These include, CH
4
(methane), O
2

(oxygen) and the so-called acid gases, H
2
S (hydrogen sulfide) and CO
2
(carbon dioxide). The
solubility of these gasses decreases as the temperature rises and increases with pressure in
water-based solutions. At about 2438 m (8000 ft) the solubility of methane in water is 100 times
greater than at surface and at 6095 m (20000 ft) it is about 300 times greater
3
. Furthermore,
water at temperatures above 100C can actually lose its polar nature, enabling it to dissolve a
larger portion of non-polar compounds such as hydrocarbons.

Both solid and gaseous solutes may exist in solution in concentrations beyond their saturation
levels; a supersaturated solution has no solids or bubbles. It cannot contain solid impurities and it
cannot be agitated. For our purposes, the term supersaturation refers to a solution containing a
high enough concentration of solute (usually a salt) that crystals appear in the fluid.


2.4.4 Oil Solubility

Most base oils are a blend of non-polar hydrocarbons. They act as good solvents for many non-
polar compounds. These include asphalt tar, wax and resins (extrusions from tree bark). For this
reason resins and waxes are used as bridging solids in oil reservoirs. The solubility of some
substances is increased in oils of higher aromatic content. Elastomers (rubber components) are
an example of this. Ionic salts are insoluble in oil-based systems. Gases have an insignificant
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amount of intermolecular bonding strength when compared to ionic crystals. For this reason most
gases are miscible in both water-based and oil-based fluids.

Generally, the solubility of gas in oil is influenced (increased) by pressure, to a much greater
degree than in water. This makes the detection of a gas hydrocarbon influx more difficult in oil-
based fluids. The saturation point of a gas in a liquid is sometimes called the bubble point. An
equal amount of gas dissolved (as opposed as entrained) in an oil-based fluid will not reach the
bubble point until a much shallower depth than gas dissolved in a water-based fluid. In fact, the
solubility of gas in oil is unlimited for any specific temperature condition, whenever the pressure is
higher than the critical pressure for that gas.


2.4.5 Dispersion and Dispersability

Dispersion is a two phase system where one phase consists of finely divided particles distributed
through a bulk phase. The term dispersability refers to the inherent ability of the internal phase
particles to accomplish this. Under controlled conditions the uniformity of a dispersion can be
increased by wetting or dispersing agents. Table 2.8 shows the possible combinations of gas,
liquid and solids (our preceding definition of the states of matter) that can form dispersions.

Table 2.8
The Possible Dispersion Systems

Internal Phase External Phase Example
Gas Liquid Foam
Solid Gas Aerosol (smoke)
Gas Solid Styrofoam
Liquid Gas Fog
Liquid Liquid Emulsions
Solid Liquid Paint
Solid Solid Concrete

Various derivatives of the word disperse, are used through this manual. For our purposes, the
term disperse can be thought of as the sub-division of particle aggregates.

In water-based systems, both ionic and covalent compounds may be easily dispersed even if they
do not dissolve. Dispersion is dependant on residual surface charges, which interact with the
polar water molecules. For example, the negative charge on the surface of most clays attracts the
positive end of water, molecules, forming a tightly bonded layer of water around the clay particle.
Other available water molecules may form successive layers contributing to particle separation
and an increased degree of dispersion. This phenomenon is sometimes called water wetting.
Brownian motion, induced movement of the particles contributes to greater uniformity. (Brownian
motion is caused by the impact of moving liquid molecules on the particles; it increases as the
temperature increases.)

Most polar or charged substances disperse readily in water. Barite, sometimes called inert, is a
good example. Non-polar substances such as oil do not. The molecules in oil have a greater
affinity for each other and tend to coalesce. That is, they are immiscible in water. Non-polar
substances that do not actually dissolve in base oils are usually readily dispersible in them.
Gilsonite is an example. Certain surfactants can cause polar substances such as clays to behave
as through they were non-polar, enabling them to disperse in oil.
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2.4.6 Colloidal Systems and Suspensions

A colloid is a very fine particle. One definition (Webster) lists three criteria necessary to qualify
as a colloid. A substance must be in such a state of division as to:

1. Prevent passage through a semi-permeable membrane
2. Consist of particles too small for resolution with an ordinary light microscope.
3. In solution or suspension fail to settle out and diffracts a beam of light.

H. van Olphen
4
provides a good definition of the term colloidal solution and the distinction
between it and a suspension, as the terms relate to clay particles. Early researchers noted that
clay appears to dissolve in water just like common salt. However, observations of clay solutions
made with ultra-microscopes showed particles against the dark field of observation. (The image in
an ultra-microscope results from indirect light being reflected off the particle and into the objective
lens). These particles were moving due to a translational Brownian motion, indicating they were
indeed particles. The image intensity varied, indicating the particles were rotating and therefore
not spherical.

Fig. 20: Transmission EM of clay colloid



Hence, the solution was actually a dispersion of very fine particles. Such dispersion is now
called a colloidal solution or sol, if the dimensions of the particles are such that they do not settle
within a reasonable time. If the particles settle more rapidly, the dispersion is called a
suspension. The word settle contradicts point 3 of Websters definition. The distinction between
a colloidal solution and a suspension is entirely arbitrary; there is no difference in principle.
4

The borderline between colloidal solution and suspension is usually chosen at an equivalent
spherical radius or Stokes radius of 1 m. Today, a colloidal dispersion is said to contain particles
ranging in size from 1 mm (10
-3
m) down to 1 nm (10
-9
m). A colloidal system or dispersion may
exist in all of same forms or possibilities as the dispersion system as outlined in Table 2.8. The
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dispersed particles exist in an internal or discontinuous phase, within an external or continuous
phase. In colloidal systems they are called kinetic units, and may be gas, liquid, solid or
macromolecules such as polymers. To refer to the dispersed particles as colloids might be
confusing; a water-in-oil emulsion can be a colloidal system, but water is seldom referred to as a
colloid. The particles in hydrous (water is the external phase) colloidal systems fall into two main
classifications:

1. HYDROPHOBIC COLLOIDS: This term is somewhat misleading since the particles do
not actually repel the solvent (for our purposes, water) as the term suggests. An example
is a dispersion of clay particles. The bar represents 1 m.



2. HYDROPHILLIC COLLOIDS: These particles display a remarkable greediness for water,
for example polymeric gums. It is recognized that most dissolved natural and synthetic
gums can be considered true solutions, therefore hydrophilic colloids are sometimes
called polyelectrolyte solutions. (An exception is most cross-linked polymers, which
usually do not completely dissolve).
5


Emulsions and foams are other examples of colloidal systems, which make up drilling fluids. In a
water-in-oil emulsion, brine droplets less than a m in diameter constitute the internal phase.

Table 2.9
Size Versus Surface Area In Cubes

Cube dimension # Of Cubes Surface Area
1.0 cm 1 6 cm
2

1.0 mm 1000 60 cm
2

0.01 mm 1x10
9
6000 cm
2

1.0 m 1x10
12
6 m
2

0.01 m 1x10
18
60 m
2


Table 2.9 shows how the surface area of 1-cm cube increases as the cube is divided into
increasingly smaller cubes. In the colloidal size range, the surface area of the particles is so much
larger than their relative volume, that unusual phenomena occur in solutions where they are
present. When the viscosity of the external phase is high enough, gravity may be unable to cause
settling. The large surface area also immobilizes much more water. Crystalline water is more
viscous. The effect also promotes an increased degree of particulate associations and
interactions. This can impart increased viscosity and gelation characteristics to even a
hydrophobic colloidal system even when the particles, such as barite particles are relatively
inert.

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2.4.7 Equilibrium and Precipitation

Physical equilibrium is the term used when two or more phases of a system change at the
same rate so that the net change in the system is zero. An example is the liquid-to-vapor, vapor-
to-liquid interchange in an enclosed system. This system reaches equilibrium when the number
of molecules leaving the liquid is equal to the number entering it.

Chemical equilibrium is a condition in which a reaction and its opposite or reverse reaction
occur at the same rate, resulting in a constant concentration of reactants. The double arrow is the
customary symbol for an equilibrium reaction. For example, ammonia in water creates ammonium
hydroxide. The reaction is at equilibrium when ammonia molecules form and ammonium
hydroxide decompose at equal rates.

NH
3
+ H
2
O NH
4
+
OH
-


Or for water:

H
2
O H
+
+ OH
-


What this means is that in an H
2
O solution, each water molecule does not have to keep all of its
component ions indefinitely. Molecules may exchange ions as often as they wish.

A number that relates the concentrations of starting materials and products of a reversible
chemical reaction to one another is called the equilibrium constant, K. At a given temperature,
K is constant regardless of the quantities of the substances. When K is known, it is often possible
to predict concentrations of products, when those of the starting materials are known.

Precipitation occurs when a solid material falls out of solution. If a hot salt solution (in water) is
fully saturated with salt, as it cools salt will precipitate out of solution, the scientific term for this is
crystallization. It can also describe the process whereby two types of dissolved ions or molecules
combine to form an insoluble (solid) compound called a precipitate. Sometimes the reaction is
indicated by a downward vertical arrow although precipitates do not necessarily drop out of a
viscofied suspension.

CaSO
4
+ Na
2
CO
3
CaCO
3
+ Na
2
SO
4


The precipitation of various substances is used in both the chemical analysis and in the removal
of contaminating ions from drilling fluids. A common example is the treatment of anhydrite
(CaSO
4
) contamination.

Precipitation may cause desirable components of drilling fluids to drop out of suspension. An
example occurs with Xanthan Polymer in the presence of both high calcium and pH.

Drilling fluids contain so many ionic species and are subject to so many influences (temperature,
pressure, contaminants) that it can be extremely difficult to predict reactions and events, including
saturation point, equilibrium and precipitation.

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2.4.8 Drilling Fluids: Multi-phase Homogenates

Table 1.1 provided a general classification of drilling fluids based on their fluid phase. Actually
most drilling fluids are multi-phase systems or homogeneous or uniformly blended mixtures.

Probably the most complex example is an oil-based fluid. Describing the constituents and phases
of an oil-based fluid uses much of the terminology and concepts explained in the previous three
sections. Up to four physical states exist: water, oil, solids and gas. The fluid qualifies as a
colloidal solution, specifically an emulsion according to our preceding definition. The oil is the
external phase and the water, solid and any entrained gas are the internal phases. Both oil and
water are solvents, the water containing dissolved salts up to saturation and the oil containing
polymers, gasses and other solutes. After viscosification, the introduction of larger sized
commercial solids like barite and also native solids, qualifies the fluid as a proper suspension
also.

All of the constituents of the fluid work together to provide its various properties. These in turn
contribute to the functions of the fluid as outlined in Chapter One. When analyzing a sample, the
drilling fluid engineer attempts to discern the concentrations of all the constituents. This is done
through specific tests, or by extrapolating from calculations. After proper analysis, modifications
may then be made to the individual concentrations of constituents, which will change the
properties and enhance the ability of the fluid to perform its functions.


2.5 CHEMICAL CALCULATIONS

2.5.1 Molarity and Normality

Stoichiometry is the aspect of chemistry that deals with the quantitative relationships among
reactants and products. The mole concept is used for solving problems in stoichiometry.
Balanced equations are very important because they provide the mole ratios. These ratios can be
used to convert quantities of reactants or products to moles, grams, or number of molecules.
Physicists, and some chemists, measure the masses of individual atoms in kg, g, or atomic mass
units. For most chemists, however, the mass of a single atom is inconveniently small and the
molar mass (mole) of a substance is used. The molar mass of an atom is the mass of a very
large number of identical atoms, one mole of atoms. One mole of atoms is by definition that
number of atoms which exist in exactly twelve grams of carbon of isotopic mass twelve (
12
C). This
number is called the Avogadro number, N
A
, and the best current determination of its value is
6.02 x 10
23
. This mole is just a number. So 1 mole = 6.02 x 10
23
particles (either atoms or
molecules).
Mole (mol) =
MW
g weight ) (

MW = molecular (or atomic) weight
Molar Atomic Masses of Elements
The molar mass of an atom is simply the mass of one mole of identical atoms. However, most of
the chemical elements are found on earth not as one isotope but as a mixture of isotopes, so the
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atoms of one element do not all have the same mass. Chemists therefore distinguish the molar
atomic mass of an isotope, which is the mass of one mole of the identical atoms which form that
isotope, from the molar atomic mass of an element, which is the mass of one mole of the atoms
of the various isotopes of that element having the natural abundances as they are found on earth.
For many elements the variation found in the natural abundances limits the accuracy with which
the molar atomic mass of that element can be known.

Table 2.10: Relative Atomic Masses of the Chemical Elements

Element Symbol Atomic
weight
Atomic
number
Oxidation
states (valency)
Density
ACTINIUM Ac 227,0278 89 3 10,07
ALUMINUM Al 26,98154 13 3 2,7
AMERICIUM Am (243) 95 6;5;4;3 13,6
ANTIMONY Sb 121,75 51 5;3;-3 6,68
ARGON Ar 39,948 18 1,784*
ARSENIC As 74,9216 33 5;3;-3 5,72
ASTATINE At (210) 85 7;5;3;1;-1
BARIUM Ba 137,33 56 2 3,5
BERKELIUM Bk (247) 97 4;3
BERYLLIUM Be 9,01218 4 2 0,53
BISMUTH Bi 208,9804 83 5;3 9,8
BORON B 10,81 5 3 2,34
BROMINE Br 79,904 35 5;1;-1 3,12
CADMIUM Cd 112,41 48 2 8,65
CALCIUM Ca 40,08 20 2 1,55
CALIFORNIUM Cf (251) 98 3
CARBON C 12,011 6 4;2;-4 2,62
CERIUM Ce 140,12 58 3;4 6,78
CESIUM Cs 132,9054 55 1 1,87
CHLORINE Cl 34,453 17 7;5;3;1;-1;-3 3,17*
CHROMIUM Cr 51,996 24 2;3;6 5,8
COBALT Co 58,9332 27 2;3 8,9
COPPER Cu 63,546 29 1;2 8,96
CURIUM Cm (247) 96 3 13,6
DYSPROSIUM Dy 162,5 66 3 8,54
EINSTEINIUM Es (252) 99
ERBIUM Er 167,26 68 3 9,05
EUROPIUM Eu 151,96 63 3;2 5,26
FERMIUM Fm (257) 100
FLUORINE F 18,9984 9 -1 1,696*
FRANCIUM Fr (223) 87 1
GADOLINIUM Gd 157,25 64 3;2 7,89
GALLIUM Ga 69,72 31 3 5,91
GERMANIUM Ge 72,59 32 4 5,32
GOLD Au 196,9665 79 3;1 19,3
HAFNIUM Hf 178,49 72 4 13,1
HELIUM He 4,0026 2 0,1787*
HOLMIUM Ho 164,9304 67 3 8,8
HYDROGEN H 1,0079 1 1 0,0899*
INDIUM In 114,82 49 3 7,31
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Element Symbol Atomic
weight
Atomic
number
Oxidation
states (valency)
Density
IODINE I 126,9045 53 7;5;1;-1 4,92
IRIDIUM Ir 192,22 77 6;4;3;2 22,5
IRON Fe 55,847 26 2;3 7,86
KRYPTON Kr 83,8 36 3,74*
LANTHANUM La 138,9055 57 3 6,7
LAWRENCIUM Lr (260) 103
LEAD Pb 207,2 82 4;2 11,4
LITHIUM Li 6,941 3 1 0,97
LUTETIUM Lu 174,967 71 3 9,84
MAGNESIUM Mg 24,305 12 2 1,74
MANGANESE Mn 54,938 25 2;3;4;6;7 7,43
MENDELEVIUM Md (258) 101
MERCURY Hg 200,59 80 2;1 13,53
MOLYBDENUM Mo 95,94 42 2;3;4;5;6 10,2
NEODYMIUM Nd 144,24 60 3 7
NEON Ne 20,179 10 0,901*
NEPTUNIUM Np 237,0482 93 6;5;4;3 20,4
NICKEL Ni 58,7 28 2;3 8,96
NIOBIUM Nb 92,9064 41 3;5 8,55
NITROGEN N 14,0067 7 5;4;3;2;-3 1,251*
NOBELIUM No (259) 102
OSMIUM Os 190,2 76 8;6;4;3;2 22,4
OXYGEN O 15,9994 8 -1;-2 1,429*
PALLADIUM Pd 106,4 46 4;2 12
PHOSPHORUS P 30,97376 15 5;4;3;-3 1,82
PLATINUM Pt 195,09 78 4;2 21,4
PLUTONIUM Pu (244) 94 6;5;4;3 19,8
POLONIUM Po (209) 84 4;2 9,4
POTASSIUM K 39,0983 19 1 0,86
PRASEODYMIUM Pr 140,9077 59 3;4 6,77
PROMETHIUM Pm (145) 61 3 6,475
PROTACTINIUM Pa 231,0359 91 5;4 15,4
RADIUM Ra 226,0254 88 2 5
RADON Rn (222) 86 9,91*
RHENIUM Re 186,207 75 7;6;4;2;-1 21
RHODIUM Rh 102,9055 45 4;3;2 12,4
RUBIDIUM Rb 85,4678 37 1 1,53
RUTHENIUM Ru 101,07 44 8;6;4;3,2 12,2
SAMARIUM Sm 150,4 62 3;2 7,54
SCANDIUM Sc 44,9559 21 3 3
SELENIUM Se 78,96 34 6;4;-2 4,8
SILICON Si 28,0855 14 4 2,33
SILVER Ag 107,868 47 1 10,5
SODIUM Na 22,98977 11 1 0,97
STRONTIUM Sr 87,62 38 2 2,6
SULFUR S 32,06 16 6;4;2;-2;-4 2,07
TANTALUM Ta 180,9479 73 5 16,6
TECHNETIUM Tc (98) 43 7 11,5
TELLURIUM Te 127,6 52 6;4;-2 6,24
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Element Symbol Atomic
weight
Atomic
number
Oxidation
states (valency)
Density
TERBIUM Tb 158,9254 65 4;3 8,27
THALLIUM Tl 204,37 81 3;1 11,85
THORIUM Th 232,0381 90 4 11,7
THULIUM Tm 168,9342 69 3;2 9,33
TIN Sn 118,69 50 2;4 7,3
TITANIUM Ti 47,9 22 3;4 4,5
TUNGSTEN W 183,85 74 6;5;4;3;2 19,3
UNNILHEXIUM Unh (263) 106
UNNILPENTIUM Unp (262) 105
UNNILQUADIUM Unq (261) 104
URANIUM U 238,029 92 6;5;4;3 18,9
VANADIUM V 50,9415 23 2;3;4;5 5,8
XENON Xe 131,3 54 5,89*
YTTERBIUM Yb 173,04 70 3;2 6,98
YTTRIUM Y 88,9059 39 3 4,5
ZINC Zn 65,38 30 2 7,14
ZIRCONIUM Zr 91,22 40 4 6,49


Chemists deal with elements as they are naturally found. In actual fact it is very difficult to
separate isotopes. Chemists like to deal with the atomic mass or atomic weight of 1 mole of a
substance. The weighted molar atomic mass of an element as it naturally occurs will be referred
to simply as the atomic mass of the element from now on.
Example 1:
What is the atomic mass of Pb? Look on the periodic table and find Pb. You'll find the mass
number listed as 207.2.

1. One atom of Pb weights 207.2 amu.
2. One mole of Pb atoms weights 207.2 grams. That is 1 mole or 207.2 grams of Pb
contains 602,000,000,000,000,000,000,000 atoms of Pb.

Example 2:
The sum of individual atoms can be used to find the mass of a molecule. The mass of hydrogen
peroxide, H
2
O
2
would be calculated like this:

1. H
2
O
2
has 2 hydrogen atoms and 2 oxygen atoms in it.
2. Therefore the mass is 2 x H + 2 x O = 2 x 1.01 amu + 2 x 16.00 amu = 2.02 + 32.00 =
34.02 amu. So one molecule of hydrogen peroxide weighs in at 34.02 amu. A mole of
hydrogen peroxide would weigh 34.02 grams.

The periodic table provides you with individual atomic masses. If you know the number and type
of elements in a molecule you can add up the individual masses to find the molecular mass or
molecular weight.

Example 3:
Find the molecular mass of calcium phosphate, Ca
3
(PO
4
)
2


The molecule has 3 calcium atoms, 2 phosphate atoms and 8 O atoms in it. Stop and verify this
for yourself. The Ca has a subscript 3 with it. The P has an assumed 1 and the O has a 4.
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However the PO
4
group has a set of brackets around it with a subscript 2. The 2 means multiply
everything inside the brackets by 2. So we end up with the 2 P and 8 O atoms.

Calculation: 3 x Ca = 3 x 40.08 amu = 120.24 amu
2 x P = 2 x 30.97 amu = 61.94 amu
8 x O = 8 x 16.00 amu = 128.00 amu

The total of the individual types of atoms is 120.24 amu + 61.94 amu + 128.00 amu = 310.18
amu.
One molecule of calcium phosphate weighs 310.18 amu and a mole of it would weigh 310.18
grams.

Example 4:
Find the mass in grams of 1.0 mole of NaOH and then find how many moles are in 500g of
Caustic soda.

Add up the atomic weights of the atoms using the periodic table:
Na O H
22.99 + 15.99 + 1.008 = 39.988

1 mole of NaOH weighs 39.988g

The number of moles in 500 g of NaOH is calculated by:
500 g / 39.988 = 12.505 moles

These examples show the advantage of using atomic mass units when individual atoms and
molecules are considered.

The term molarity is indicated by a capital M. A molar solution refers to a concentration in which
one mole (molecular weight in grams) of a substance is dissolved in enough solvent to make one
liter of final solution. Molar quantities are proportional to the molecular weights of substances.
Because molar weights of different substances contain the same number of molecules, equal
volumes of one molar solution will contain the same number of molecules of the solute. For
example, if 1 mole of potassium hydroxide is needed for a given reaction, one can use 1 liter of a
one molar (1M) solution or 2 liters of a 0.5 M solution. Molarity is a weight/volume expression.
Because one mole of HCl weighs 39.99 g, 1M HCl = 39.99 g/l.

Molarity (M) =
V
mole


mole = moles of solute
V = volume of solution (litres)

The term molality (m) is indicated by a lower case m. A molal solution refers to a concentration
in which the amount of solute is stated in moles and the amount of solvent (not final solution) is
stated in kg. One mole if NaCl added to 1 kg of solvent is a 1 molal concentration.

Molality (m) =
W
mole


mole = moles of solute
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W = weight of sovent (kg)

The term normality (N) is often used to express concentrations in solutions, especially in the
reagents used in our chemical analysis. An understanding of the term equivalent weight is
necessary to explain normality. In its simplest form, the term equivalent weight (EW) means the
atomic or molecular weight of an ion, atom or molecule divided by its (charge) valency. The
atomic weight of Mg
2+
is 24.30 and its valency is 2, making its equivalent weight 12.15.

Normality (N) =
V
equiv
equiv (eq) =
EW
g weight ) (
EW =
n
MW


equiv = equivalents of solute
V = volume of solution (litres)
Weight = weight of solute
EW = equivalent weight
MW = molecular (or atomic) weight
n = number of H
+
, OH
-
, or e
-
involved in the reaction considered
There is a very simple relationship between normality and molarity:
N = n M
Normality then, refers to a solution having 1 gram equivalent per one liter of final solution. A 1
normal solution contains one equivalent weight of the solute in grams dissolved in one liter of final
solution. For substances with a valency of one, a 1N solution is identical to a 1M solution. For
substances with a valency of two, then a 1M solution is twice the strength of a 1N solution.
For an acid or basic reaction, n is the number of H
+
or OH
-
provided by a formula unit
of acid or base.
Example 1: A 3M H
2
SO
4
solution is the same as a 6N H
2
SO
4
solution.
A 0.01M HCl solution is the same as 0.01N HCl solution.
Example 2: A 1M Ca(OH)
2
solution is the same as a 2N Ca(OH)
2

solution.
A 5N KOH solution is the same as 5N KOH solution.

For a redox reaction, n is the number of e
-
involved.
Example 3: MnO
4
-
+ 5e + 8H
+
Mn
+2
+ 4 H
2
O
EW (KMnO
4
) =
5
MW
= 158/5 = 31.6
A 1M KMnO
4
solution is the same as a 5N KMnO
4
solution.
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Example 4: MnO
4
-
+ 3e + 2H
2
O MnO
2
+ 4OH
-

EW (KMnO
4
) =
3
MW
= 158/3 = 52.7
A 1M KMnO
4
solution is the same as a 3N KMnO
4
solution.

For a precipitimetric and chelometric reaction, n depends on the stoichiometry of
reaction.
Example 5: Ag
+
+ Cl
-
AgCl
EW (AgNO
3
) = MW (AgNO
3
) = 169.9
A 1M AgNO
3
solution is the same as a 1N AgNO
3
solution.
Example 6: (EDTA)
-2
+ Ca
+2
Ca(EDTA)
EW (Na
2
(EDTA)) = MW (Na
2
(EDTA)) = 370.2
A 1M Na
2
(EDTA) solution is the same as a 1N Na
2
(EDTA) solution.

Note: sometimes molar and normal concentrations are expressed as fraction of 1M or 1N
solutions:

A N/50 H
2
SO
4
solution is the same as a 1/50 = 0.02N H
2
SO
4
solution.

A M/100 Na
2
(EDTA) solution is the same as a 1/100 = 0.01M Na
2
(EDTA) solution.


2.5.2 Concentrations in Solutions and Suspensions

All of the constituents of drilling fluids are reported as concentrations. This includes soluble salts
and polymers as well as insoluble materials such as drilled solids, barite and bentonite.

Knowing how certain concentrations are influencing fluid properties enables a drilling fluid
engineer to effectively modify his system to suit the hole conditions being encountered. By
combining specific concentrations with a known specific gravity, mass balance analysis can
become extremely accurate. This helps in analyzing the effectiveness of products and planning
future wells.

The petroleum industry uses both the S.I. (International System) and Imperial System of units for
quantifying concentrations. Usually one of three methods is used to describe a volume or weight
relationship between the fluid phase and either the solid phase or a solute. These are:

1. volume/volume (v/v)
2. weight/volume (w/v)
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3. weight/weight (w/w)

1. Volume/Volume

The v/v relationship is the easiest to understand. This is used when adding liquid additives to a
system. It is reported as, gal/bbl, ml/L, L/m
3
or sometimes %v/v, as in 8% spotting fluid.

NOTE: to avoid errors in concentrations when mixing liquid additives, consider the final volume of
fluid required.



Example 1:

Exactly 8% spotting fluid is to be mixed to net exactly 12 m
3
(12000 L) of final fluid. (Ignore any
barite requirement).

1. Starting volume:
12000 (12000 x 0.08) = 11040 L
2. Volume of spotting fluid:
12000 L 11040 L = 960 L

Adding 8% of 12 m
3
to 12 m
3
of water would result in 13 m
3
final volume with a concentration of
7.4%!

The v/v relationship is also used to describe retort analysis. In oil-based fluids it is actually v/v/v or
oil/water/solids. Often v/v concentrations are expressed as percent. It is important to state that it
is a volume % or % by volume, not a weight %. The amount of oil retained on cuttings us
usually expressed as v/v, L/m
3
.

2. Weight/Volume

The best method of defining concentration of solute in solution or solids in suspension is by the
w/v relationship. The familiar units in the Imperial system are pounds per barrel (ppb). In S.I.
system mg/L is used to describe minute units and kg/m
3
or g/L are used when defining large
concentrations. The best aspect of the S.I. system is that all units of weight and volume are
multiples of 10. No conversion factors are necessary. For example, when pilot testing, if the best
concentration is 2.6 grams of polymer in one liter (almost a quart) of testing fluid (w/v = g/l), then
2.6 kg/m
3
of product should be added to the system. The w/v relationship is the easiest method to
use in mass-balance calculations since weight can refer to solute and solid.

1000 mg/L = 1.0 g/L = 1.0 kg/m
3


3. Weight/Weight

The weight of solute per weight of solution, w/w relationship is another common method of
reporting concentrations. Minute concentrations expressed in parts per million (ppm) usually
(not always) implies ppm as a w/w relationship. Salt solutions and completion brines are often
expressed in terms of %w/w for example a 4% solution of KCl. This usually implies a w/w
relationship and can be converted to ppm by the following formula:

10000 ppm (w/w) = 1% by weight.
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When a w/w relationship is used to express concentrations, the following points must be stressed:
when referring to a solute as a percentage concentration it is appropriate to state % by
weight.
ppm does not have to mean w/w
ppm is not the same as mg/l except when the s.g. of a solution is 1.0.


API RP 45 states: It is the recommendation of the committee that mg/L be adopted as the unit of
concentration and the value of s.g. be included as an integral part of the water analysis. This
practice was recommended because too many independent labs recorded erroneous
concentrations, because they used mg/L and ppm interchangeably. The recommendation
provides adequate data for those who must use the w/w relationship.


2.5.3 Converting and Calculating

Converting from one method of reporting concentrations to another or one system of units to
another usually requires the specific gravity of a substance. Table 2.11 shows the specific gravity
of some common drilling fluid additives. Listed below are some expressions which are useful in
drilling fluid engineering. Remember, when adding any soluble substance to a solution which is
not saturated, the volume increase is not linear. Tables must be used when adding salts.


Table 2.11: Specific Gravity Of Common Drilling Fluid Additives

Water Soluble Additives

Water Insoluble Additives
Product Specific Gravity

Product Specific Gravity
NaOH 2.13

BaSO
4
4.2-4.3
NaCl 2.16

CaCO
3
2.7-2.95
NaCO
3
2.51

Galena (PbS) 6.5
Na
2
CO
3
2.2

Diesel Oil 0.84-0.9
CaCl
2
2.51

Clay 2.4-2.7
KCl 1.99

Cement 3.1-3.2
Al
2
(SO
4
)
3
2.71

FeCO
3
3.7
CaSO
4
2.96



1. Convert from mg/l to ppm and back:

mg/L = ppm x s.g. ppm =
. .
/
g s
L mg


Example 1:

300 mg/L of CaCO
3
corresponds to 300/2.65 = 113.2 ppm of CaCO
3




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2. Convert from density to volume in solution (this does not apply to soluble substances):

d =
V
m
V =
d
m
m = Vd

1.0 g/cm
3
= 1.0 g/ml = 1.0 kg/L = 1.0 t/m
3

d = density (or s.g.), g/cm
3
or kg/L
V = volume, L or m
3

m = mass, kg or t

Example 2:

Calculate the volume increase by addition of 15 t of barite:

V = (15 t) / (4.25 t/m
3
) = 3.5 m
3


3. Convert from %v/v to %w/w to %w/v:

%w =
F
M
d
d v %
%v =
M
F
d
d w %


%v = volume percentage of material
%w = weight percentage of material
d
M
= specific gravity of material (g/cm
3
)
d
F
= specific gravity of fluid
kg/m
3
= %wd
F
10 %w =
10
/
3

F
d
m kg


kg/m
3
= %vd
M
10 %v =
10
/
3

M
d
m kg


kg/m = concentration of material


4. Concentration and quantity calculations:

There are several methods available for calculating concentrations based on chemical reactions.
The following example is used to explain one procedure.

Example 1:
A 150 m
3
drilling fluid system contains 830 mg/l Ca
+2
. How many kg of soda ash is required to
precipitate all of the calcium?

First balance the equation as explained in the preceding text:

Na
2
CO
3
+ Ca
2+
CaCO
3
+ 2Na
+

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It is true that Na
+
does not react with the Ca
+2
, but since the treatment is made with Na
2
CO
3
and
not CO
3
-2
, the 2Na
+
is a factor.

This equation is stating that 1 mole of CO
3
-2
will react with exactly 1 mole of Ca
2+
. Thus, using the
periodic table the weight ratios of each may be determined:

MW (Na
2
CO
3
) = 106 MW (Ca) = 40

The ratio is 106/40. This means 106 g (or moles) of Na
2
CO
3
will always combine with 40 g (or
moles) of Ca
+2
. The concentration of calcium, 830 mg/l is the same as 0.83 kg/m
3
. Thus:

Na
2
CO
3
=
40
106
83 . 0 = 2.20 kg/m
3

Therefore 2.20 kg/m
3
of soda ash is required to treat out all of the calcium.

Example 2:
Calculate molar concentration of 96% sulfuric acid (H
2
SO
4
), having density of 1.835 g/cm
3
.
(MW = 98)

M =
MW
d 10 %
N =
EW
d 10 %


% = %w/w concentration
d = specific gravity of solution (g/cm
3
)
MW = molecular weight of substance
EW = equivalent weight of substance

Concentration of solution is therefore approx 18M or 36N.


5. Titrations and dilutions:

When a diluting a solution, the number of moles of substance remains the same: only the volume
of solvent changes. For that reason, the following formula can be used for diluting solutions:

V
1
N
1
= V
2
N
2


V = volumes of solutions (ml or L)
N = normal concentrations (not molar!)

That formula is also used when titrating substances: at the endpoint of titration the number of
equivalents of titrating solution is equal to that of titrated substance.

Example 1:
Prepare 500 ml of 0.01N solution, stating from 5N one.

500 ml0.1N = V5N V = 10 ml

Take 10 ml of 5N solution and dilue with water to 500 ml.
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Example 2:
5.0 ml of AgNO
3
0.1N have been used to titrate 1 ml of filtrate. What is the concentration of
chloride ions?

5.0 ml0.1N = 0.5 meq AgNO
3
= meq Cl
-
(= mmol Cl
-
)

mgCl
-
in 1.0 ml of filtrate = mmolMW = 0.535.45 = 17.72 mg

mg/L Cl
-
= 17.721000 = 17720 mg/L


2.6 ACID AND BASES

In 1923, J. N. Bronsted in Denmark and T. M. Lowry in England independently, and almost
simultaneously, proposed the modern "protonic" or Bronsted-Lowry theory of acid-base behavior.
According to the Bronsted-Lowry concept, an acid is any compound or ion which can give up a
proton, while a base is any compound or ion which can accept a proton.
A molecular species which can either accept or give up a proton is said to be amphiprotic. Thus
the water molecule is amphiprotic, since it can give up a proton, H
2
O H
+
+ OH
-
, to form the
hydroxyl ion OH
-
. Alternatively, water can accept a proton to form the hydronium ion H
3
O
+
,
according to the equation H
+
+ H
2
O H
3
O
+
. The above two equations can be combined to give
the dissociation equation for water: 2H
2
O H
3
O
+
+ OH
-
.
The Bronsted-Lowry concept is an extension of the Arrhenius concept in that bases, being
sources of hydroxide, can accept protons; on the other hand acids, being sources of protons, can
accept hydroxide. Ammonia and amines will also accept protons to form the corresponding
ammonium ions, so the existence of NH
4
OH is no longer necessary to explain the action of
ammonia as a base. The Bronsted-Lowry concept also is useful in protonic solvents other than
water, such as liquid ammonia or glacial acetic acid, where the Arrhenius concept is not useful.
We will, however, generally confine our discussion to aqueous solutions because they are so
much more important.
Lewis Acids and Bases
The basic principles of the Lewis theory of acid-base behavior were also set down in 1923, by
the American physical chemist G. N. Lewis. The Lewis definitions of acids and bases are even
more inclusive than the Bronsted definitions. The Lewis definitions are that an acid is an
electron-pair acceptor and a base is an electron-pair donor.

H
N
H
H


Since a base like ammonia (above) has a lone pair of electrons, it can be considered to "donate"
them to a proton in forming the conjugate acid NH
4
+
. The Lewis definitions are used to explain the
effect of compounds such as AlCl
3
, which acts as an acid in non-aqueous organic solvents, on
organic reactions. In protonic solvents, however, they are far less useful than are the Bronsted
definitions.


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2.6.1 pH
A Simple Definition
pH is a logarithmic measure of hydrogen ion concentration, originally defined by Danish
biochemist Sren Peter Lauritz Srensen in 1909:

pH = - log[H
+
]

where log is a base-10 logarithm and [H
+
] is the concentration of hydrogen ions in moles per liter
of solution (M). According to the Compact Oxford English Dictionary, the "p" stands for the
German word for "power", potenz, so pH is an abbreviation for "power of hydrogen".

The pH scale was defined because the enormous range of hydrogen ion concentrations found in
aqueous solutions make using H
+
molarity awkward. For example, in a typical acid-base titration,
[H
+
] may vary from about 0.01M to 0.0000000000001M. It is easier to write "the pH varies from 2
to 13".

The hydrogen ion concentration in pure water around room temperature is about 1.0 10
-7
M. A
pH of 7 is considered "neutral", because the concentration of hydrogen ions is exactly equal to
the concentration of hydroxide (OH
-
) ions produced by dissociation of the water (K
w
).

K
w
= [H
+
][OH
-
] = 10
-7
M x 10
-7
M = 10
-14
M
2

Increasing the concentration of hydrogen ions above 1.0 10
-7
M produces a solution with a pH
of less than 7, and the solution is considered "acidic". Decreasing the concentration below 1.0
10
-7
M produces a solution with a pH above 7, and the solution is considered "alkaline" or "basic".
So:
0 < pH < 7: acidic solution
pH = 7: neutral solution
7 < pH < 14: alkaline solution

pH is often used to compare solution acidities. For example, a solution of pH 1 is said to be 10
times more acidic than a solution of pH 2, because the hydrogen ion concentration at pH 1 is ten
times the hydrogen ion concentration at pH 2. This is correct as long as the solutions being
compared both use the same solvent. You can't use pH to compare the acidities in different
solvents because the neutral pH is different for each solvent. For example, the concentration of
hydrogen ions in pure ethanol is about 1.58 10
-10
M, so ethanol is neutral at pH 9.8. A solution
with a pH of 8 would be considered acidic in ethanol, but basic in water!


2.6.2 Ionization Constant

The inherent or intrinsic strength of an aqueous acid (or base) is its ability to remove a proton
from (or donate a proton to) the solvent water or other ions and molecules in aqueous solutions.
For quantitative comparisons between different aqueous acids or bases, this ability is compared
with the ability of the solvent water itself. The reaction used is the reaction which corresponds to
the ionization equilibrium whose equilibrium constant is called the ionization constant. In other
words, strengths of acids and bases are expressed quantitatively in terms of the values of their
ionization constants.
Aqueous ionization constants are quantitative measures of the tendency of the acid or base to
either donate a proton, written as H
3
O
+
or often simply H
+
, or accept a proton from water. The
greater the value of the equilibrium constant, the greater the percentage of the acid or base that
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will be in ionized form. As a generalization, we can use the value of the ionization constant equal
to 0.1 as the point of distinction between a strong acid and a weak acid. Thus a strong acid is
one for which the value of the acid ionization constant K
a
is large (>> 0.1) and a weak acid is one
for which the value of the acid ionization constant K
a
is small (<< 0.1). Likewise, a strong base is
one for which the value of the base ionization constant K
b
is large (>> 0.1) and a weak base is
one for which the value of the base ionization constant K
b
is small (<< 0.1).
HA D H
+
+ A
-
K
a
=
[ ] [ ]
[ ] HA
A H
+


BOH D OH
-
+ B
+
K
b
=
[ ] [ ]
[ ] BOH
OH B
+


AH = acid (i.e. HCl, H
2
SO
4
)
A
-
= conjugate base (i.e. Cl
-
, SO
4
-2
)
BOH = base (i.e. NaOH, NH
4
OH)
B
+
= conjugate acid (Na
+
, NH
4
+
)
There are only a few common strong acids: HCl, HNO
3
, HClO
4
and H
2
SO
4
. In the case of sulfuric
acid, H
2
SO
4
, only the ionization of the proton from H
2
SO
4
to give HSO
4
-
is strong; the ionization of
HSO
4
-
to give SO
4
2-
is not strong, but weak. Common strong bases include NaOH and KOH. On
reaction with water, CaO gives the strong base Ca(OH)
2
and for that reason CaO is considered a
strong base also, as are the oxides of sodium and potassium.
Using the values of the ionization constant as quantitative measures of acid strength is equivalent
to the qualitative statement that a strong acid is an acid for which loss of the proton to water is
essentially complete, while a weak acid is an acid for which loss of the proton is incomplete.
Likewise, a strong base is a base for which acquisition of a proton from water is essentially
complete while a weak base is a base for which acquisition of a proton is noticeably incomplete.

2.6.3 Acids and Bases

If we look at the two definitions (above) of an acidbase pair they are both telling us different
things! The ionization constant tells us exactly how strong the acid is, the pH tells us the
concentration of protons [H
+
] in solution! For Mud Engineers pH is the more important of the two,
because by knowing the concentration of [H
+
] we can figure out the concentration of the alkaline
ions in solution and base judgments of mud quality upon these results.

In general terms, acids in water solutions have the following properties.

1. Sour taste (not recommended).
2. The ability to make litmus dye turns red.
3. The ability to make other indicators change to characteristic colors.
4. The ability to react with and dissolve certain metals to form salts.
5. The ability to react with abase or alkaline to form salts

Acids are classified as strong or weak according to their ability to donate their proton or
concentration of the hydrogen ions in solution. Sulfuric acid (H
2
SO
4
) is a strong acid (pH < 1),
(higher concentration of protons), while carbonic acid (H
2
CO
3
) is a weak acid (pH = 3). Water is
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so weak that is classified as neutral (pH = 7). Strong acids are corrosive and dangerous to skin,
eyes and mucous membranes.

Common organic acids have different nomenclature but all share a common acid functionality.

Carboxylic acids (has a COOH group)
Fatty acids (has a COOH group)
Amino acids (has a COOH group)
Dicarboxylic acids (contains 2 COOH groups)


Some common organic acids

CH
3
OH
O
H OH
O
CO
2
H
H H
CO
2
H HO
H H
CO
2
H
Formic Acetic
Citric



Inorganic acids or mineral acids, include: sulfuric (H
2
SO
4
), hydrochloric (HCl), hydrofluoric
(HF), nitric (HNO
3
) and phosphoric (H
3
PO
4
).

The disassociation reaction for organic and mineral acids is the same.

CH
3
OH
O
Acetic Acid
H
+
+
CH
3
O
-
O
Proton
HCl
H
+
+ Cl
-
Hydrochloric acid Proton



In general terms, bases in water solutions have the following properties.


1. Bitter taste.
2. The ability to make litmus dye turns blue.
3. The ability to make other indicators turn characteristic colors.
4. The ability to react with acids to form salts.

Bases are classified as strong or weak according to their ability to accept a proton or decrease
the concentration of the hydrogen ions in solution. Potassium hydroxide (KOH) is a strong base
(pH = 14), while sodium bicarbonate (NaHCO
3
) is a weak base (pH=8.4). Basic solutions range in
pH from 7.1 to 14. Like acids, strong bases are corrosive to skin, eyes and mucous membranes.


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Common bases include:

NaOH KOH Ca(OH)
2
NaHCO
3
NaCO
3
Caustic soda
Sodium Hydroxide
Caustic potash
Potassium hydroxide
Hydrated lime
Calcium hydroxide
BiCarb
sodium bicarbonate
Soda Ash
Sodium carbonate



In solution they form ions that react with protons, with a net result of decreasing the proton
concentration and raising the pH.


NaOH Na
+
+ OH
-
NaHCO
3
Na
+
+ HCO
3
-



A reaction occurs with an acid


Na
+
+ OH
-
+ HCl
HOH + NaCl Na
+
+ HCO
3
-
+ HCl HOH + NaCl +CO
2



And the final equation can be written as acid + base = a salt plus water


NaOH Na
+
+ OH
-
NaHCO
3 Na
+
+ HCO
3
-
Na
+
+ OH
-
+ HCl
HOH + NaCl Na
+
+ HCO
3
-
+ HCl HOH + NaCl +CO
2
NaOH + HCl HOH + NaCl NaHCO
3
+ HCl HOH + NaCl +CO
2



In the case of carbonate and bicarbonate ions we see an additional byproduct, carbon dioxide.

As a mud engineer contact with organic bases is limited but common organic bases include
amines. The following reaction shows a basic amine reacting with an acid, notice how the
reaction is a Lewis type reaction (a base donates its electrons). The equation is base + acid =
salt.

CH
3
N
H
H
Methyl amine
+ HCl
Acid
CH
3
N
H
H
H
+ Cl
-
Amine salt


The disassociation reaction for organic and mineral bases is different! All nitrogen compounds
behave this way, including ammonia.

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Ammonia
+ HCl
Acid
H
N
H
H
H
+ Cl
-
Ammonium salt
N
H
H
H


Ammonia is an inorganic base but behaves like an organic base. As you can see when using
ammonium salts in large quantities, if an acid gas pocket is drilled we would see ammonia gas at
the surface.


2.6.4. Practical pH

pH is a value representing the alkalinity or the acidity of an aqueous solution. Mathematically pH
is defined as the negative log of the hydrogen ion concentration of a solution:

pH = -log [H
+
]


where [H]
+
is the concentration of the hydrogen ion in mol/L.

For example a 0.01M HCl solution has pH = -log[0.01] = 2

The pH of pure water is 7.0.

When adding caustic (NaOH) to a solution the concentration of H
+
ions decreases because the
product of OH
-
and H
+
is a constant (K
w
). This relationship is illustrated in Table 2.12. When
considering the effect of pH in practical terms, it is worth noting, that to raise the pH from 9.0 to
10.0 the concentration of OH
-
ions must be increased by a factor of 10 times.

Table 2.12
pH and concentration of H
+
and OH
-


pH [H
+
] [OH
-
]
14 1.0010
-14
1.0010
0

13 1.0010
-13
1.0010
-1

12 1.0010
-12
1.0010
-2

11 1.0010
-11
1.0010
-3


10 1.0010
-10
1.0010
-4
Increasing alkalinity
9 1.0010
-9
1.0010
-5

8 1.0010
-8
1.0010
-6

7 1.0010
-7
1.0010
-7
Neutral
6 1.0010
-6
1.0010
-8

5 1.0010
-5
1.0010
-9

4 1.0010
-4
1.0010
-10
Increasing acidity
3 1.0010
-3
1.0010
-11

2 1.0010
-2
1.0010
-12

1 1.0010
-1
1.0010
-13

0 1.0010
0
1.0010
-14


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A simple way to calculate pH of strong or weak acids and bases (with only one H
+
or OH
-
) having
concentration C (C > 10
-4
M) is the following:

Strong acids: pH = -log C

Example 1:
[HNO
3
] = 0.001M = C pH = -log 0.001 = 3.0

Strong bases: pH = 14 + log C

Example 2:
[KOH] = 0.5M = C pH = 14 + log 0.5 = 14 0.3 = 13.7

Weak acids: [H
+
] C K
a
pH = -log[H
+
]



Example 3:
[CH
3
COOH] = 0.5M = C K
a
= 1.810
-5
[H
+
] C K
a
= 0.003 pH 2.5

Weak bases: [OH
-
] C K
b
pH = 14 + log[OH
-
]

Example 4:
[NH
4
OH] = 0.5M = C K
b
= 1.810
-5
[OH
-
] C K
b
= 0.003 pH 14 2.5 = 12.5

The solubility of various compounds is affected by pH as well as temperature (see Figure 2.5).
This is because there is a relationship (equilibrium constant) between OH
-
and other ions besides
H
+
.


2.6.5 Alkaline Drilling Muds

As a mud engineer understanding the chemistry behind the mud system is important, it allows
you to correct problems as they are developing in the hole as a result of what is being drilled
through. A problem that occurs with great frequency is the sudden change in alkalinity of the fluid.

Drilling fluids normally have a pH in the alkaline or basic range. When considering a fluid with a
pH of 10, one can think of a fluid with 10
-10
hydrogen ions and 10
-4
hydroxyl ions. However, as we
know alkalinity can be due to ionic species other than OH
-
. For example, a 0.1N solution of
sodium bicarbonate (NaHCO
3
) has a pH of 8.4, and a 0.1N solution of sodium carbonate (NaCO
3
)
has a pH of 11.6.

Carbonate and bicarbonate species are added intentionally to treat anhydrite or cement
contamination. They may also be present unintentionally, derived from CO
2
gas, starch
degradation, biopolymer degradation, or from the solvation of the formation rock itself. Because
water has the ability to dissolve CO
2
from the atmosphere, pure water at pH 7 is a difficult state to
maintain. Why?

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To understand this we have to understand the chemistry of CO
2
, H
2
O, and OH
-
. As CO
2
dissolves
in water it forms carbonic acid but in a water solution an acid readily dissociates to give the ionic
species, a proton and a bicarbonate ion.

H
2
O + CO
2
H
2
CO
3
Carbonic acid
H
2
CO
3
H
+
+ HCO
3
-

H
2
O + CO
2
H
+
+ HCO
3
-




With the huge amounts of CO
2
in the atmosphere this explains why distilled water has a pH of
roughly 5.5.

But what happens if we have a mud system pH of 12 made up with caustic? The reaction is as
follows.


NaOH + H
2
CO
3
NaHCO
3
+ H
2
O
NaOH + CO
2
NaHCO
3
H
2
O + CO
2
H
2
CO
3

Equation 1



So as CO
2
dissolves in an alkaline mud system the caustic reacts with the acid to give sodium
bicarbonate and water. So what happens if the amount of caustic is huge?


NaOH + NaHCO
3
H
2
O + Na
2
CO
3 Equation 2



The caustic continues to react with the newly formed bicarbonate to generate water and sodium
carbonate, a very basic solution!

So lets do this again and put all these equations together. Our mud has a pH of 12 and is made
up of caustic and we have just drilled through a sweet acid gas pocket.


2NaOH + CO
2
H
2
O + Na
2
CO
3
NaOH + NaHCO
3
H
2
O + Na
2
CO
3
NaOH + CO
2
NaHCO
3
Equation 3

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So what is Equation 1 and 3 telling us? Equation 3 says that with an excess of caustic all the CO
2

will be converted to carbonates in this case sodium carbonates. If there is not enough caustic in
the mud to do this then equation 1 says that CO
2
will make sodium bicarbonate.

One important aspect to remember is those reactions that are under equilibrium (double arrows)
can go in both directions, if they are not influenced by any outside sources i.e. heat, or a large
concentration of one reagent.

Equilibrium is just that, an equal concentration of reagents and products on both sides of the
equation. Therefore if you have a water based system that introduces a huge concentration of
CO
2
, the reaction will generate an increased amount of bicarbonate ions until the system
balances itself out. If the system was acidic and you introduced large quantities of bicarbonate,
the reaction would generate H
2
O and CO
2
, until the system balanced itself. A good way to think of
equilibrium is as a type of buffered reaction, where reagents and products interchange until
there is balance.

If an outside source is influencing a reversible reaction in our case a large concentration of one
reagent, then these reactions can become essentially irreversible.


H
2
O + Na
2
CO
3
NaOH + CO
2
NaHCO
3
Equation 4
Equation 5 NaOH + NaHCO
3


Therefore, if large concentrations of CO
2
are drilled (or if large amounts of caustic have been
added), a mud system containing hydroxide ions will use up all the available hydroxide ions (or
CO
2
) to make bicarbonates. If there are still available hydroxide ions then these will react with the
bicarbonates to give carbonates. If there is an excess of hydroxide in the mud then all
bicarbonates will be convert to carbonates. If there is an excess of CO
2
in the system then all the
caustic would be used up and only bicarbonates would be present.

Another important reaction is drilling anhydrite (CaSO
4
) which causes a build up of Calcium ions;
this can cause problems with clay and mud viscosity. To treat it, sodium carbonate is added

CaSO
4

Ca
2+
+ SO
4
2-
Ca
2+
+ SO
4
2-
+ Na
2
CO
3
CaCO
3
+ Na
2
SO
4
CaSO
4
+ NaHCO
3
CaCO
3
+ Na
2
SO
4



which creates calcium carbonate that is practically insoluble in water and precipitates out of the
mud system.

The other reaction of interest is drilling cement. Cement contains calcium silicates and aluminum
silicates all of which react with water to form Ca(OH)
2
. This can cause the pH to rise dramatically
and cause serious problems with your mud system. To treat calcium hydroxide contamination you
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can add sodium bicarbonate or SAPP (sodium acid pyrophosphate) both work in the same
manner to bind free calcium in solution and remove it from the mud.


Ca(OH)
2
Ca
2+
+ 2OH
-
Ca
2+
+ 2OH
-
+ NaHCO
3
CaCO
3
+ NaOH + H
2
O
Ca(OH)
2
+ NaHCO
3 CaCO
3
+ Na
2
SO
4



NaO
P
O
O
NaO
P
O
ONa
NaO
+ Ca(OH)
2
ONa
P
O
O
ONa
P
O
O
ONa
NaO
P
O
O
NaO
P
O
O
NaO
Ca
+ 2NaOH
2


Sodium acid pyrophosphate reaction with calcium


The relationship of carbonic acid vs. bicarbonate vs. carbonate is shown graphically in figure 21
(below).

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Fig. 21:
The Distribution of Carbonate Species as a Function of pH
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
4 5 6 7 8 9 10 11 12
pH
%

M
o
l
a
r

F
r
a
c
t
i
o
n
H2CO3 HCO3- CO3--


This graph illustrates an important point, as you increase the pH with caustic the concentration of
carbonic acid falls as the bicarbonate climbs to a maximum. As you further increase the pH the
bicarbonate disappears and is replaced by carbonate ions. You can use this information to
estimate the types and concentrations of bicarbonate, carbonates and hydroxides in your mud,
this is called the Pf/Mf Method.


Pf/Mf alkalinity

If we took a pH reading of a mud sample, looking at the graph above, we could deduce the types
of ions in solution.
If pH > 11.6 (excess OH
-
), the only species you could test for would be OH
-
& CO
3
2-
.
If pH = 11.6 then the only ion present would be the CO
3
2-
(any OH
-
present would increase the
pH).
If pH < 11.6, then there would be no OH
-
(as it is all used up to convert bicarbonate to carbonate):
only HCO
3
-
& CO
3
2-
.
If the pH < 8.3 there would be only HCO
3
-
& H
2
CO
3
.
The fifth and final case would be if there were no other ions present except the hydroxide ions
you added.

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All these ion concentrations can be estimate in the field by the Pf/Mf Method. (There are other
methods that will be covered later in this manual but the theory is the same). The method
involves taking a small filtrate sample, finding the pH, adding a pH color indicator
(phenolphthalein indicator is pink above pH 8.5) and titrating (just as the pink color disappears)
with 0.02N H
2
SO
4
. The volume of acid added to make the pink disappear equals the Pf. Another
indicator is added to the filtrate sample (bromocresol green, apple green color below pH 4.5) and
acid 0.02N H
2
SO
4
is added just to the point where the liquid turns green and the volume
recorded. That second volume of acid is equal to the Mf.

Table 2.13
Pf/Mf Method Comments
If Pf = Mf [OH
-
] = (2Pf Mf) x 340 Only [OH-] ions, no contaminates
If Pf = 0 [HCO
3
-
] = Mf x 1220 Only [HCO
3
-
] ions, will have a low pH (< 8.3)
If 2Pf = Mf [CO
3
2-
] = Pf x 1200
Only [CO
3
2-
] ions, two protons needed to neutralize
CO
3
2-

If 2Pf > Mf [OH
-
] = (2Pf Mf) x 340
[CO
3
2-
] = (Mf Pf) x 1200 Both ions present. pH is > 11.6
If 2Pf < Mf [CO
3
2-
] = Pf x 1200
[HCO
3
-
] = (Mf 2Pf) x 1220 Both ions present. pH is between 11.6 and 8.3

By knowing the concentration and quantity of acid required to neutralize an alkaline solution and
by using pH dependant color indicators, the concentration of species may be calculated.

An excessive concentration of either HCO
3
-
or CO
3
2-
can become, in essence a contaminant.


2.7 SURFACE CHEMISTRY COLLOIDS REVISITED
The formal study of colloids began in the latter part of the 19th century with the studies of Thomas
Graham. The first colloids studied were gelatins and glues, and so Graham used the Greek work
kolla, meaning glue, as the root for his newly coined term.
Colloidal particles may be gaseous, liquid, or solid. They may occur in various types of
suspensions, e.g. solid/gas (aerosol), solid/solid, liquid/liquid, liquid/solid (emulsion), gas/liquid
(foam). It may be useful to observe that a suspension is any system in which small solid or liquid
particles are more or less evenly dispersed in a second medium, typically a gas or a liquid.
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Colloid examples: a) Clay, b) Cement, c) Latex or blood, d) Polymers
In the size range of colloidal particles, the surface area of the particle is so much greater than its
volume that some unusual behavior is observed, e.g. the particles do not settle out by gravity (i.e.
they neither float nor sink). Many macromolecules are at the lower limit of this size range (a
nanometer). The upper limit to colloidal particle size is commonly taken to be the size at which
the particles become visible in an optical (i.e. light) microscope (about 1 micrometer). Natural
colloidal systems include rubber latex, milk, blood, and egg-white.
Aerosols are suspensions of liquid or solid particles in a gas. The particles are often in the
colloidal size range, making many aerosols colloidal suspensions. Fog (water/air) and smoke
(C/air) are common examples of natural aerosols. Fine sprays such as those used with perfumes,
insecticides, inhalants, anti-perspirants, and paints are man-made aerosols.
An emulsion is a stable mixture of two or more immiscible liquids held in suspension by small
amounts of substances called emulsifiers. Small carbohydrate polymers like starch (which are
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themselves colloidal in size) often act as emulsifiers by coating the surfaces of the dispersed
phase and thus preventing coalescence. Such emulsifying agents are called protective colloids as
they protect the dispersed phase from coalescence and subsequent separation. Long-chain
alcohols and fatty acids can also act as emulsifiers by "solubilizing" the dispersed phase by virtue
of the formers solubility in the dispersing medium (often water).
These emulsifying agents are called detergents. Commercial polymerization reactions are often
carried out in emulsion form. Floor and glass waxes, many drugs, photographic coatings, and
paints are all examples of emulsion systems.
Foams are dispersions of gases in liquids or solids. If the gas globules are of colloidal size, the
foam is colloidal foam. Yeast breads are examples of solid foams. Shaving cream and whipped
cream are good examples of liquid foams. Useful foams for automobile seats and mattresses are
made from natural and synthetic (e.g. polystyrene, polyurethane) latexes. Metal and concrete
foams are also possible.
Any of these surfaces and interfaces can, and commonly do, occur in drilling fluids.


2.7.1 Surfaces

Surfaces can be very complex, and the majority of this science is beyond the scope of this
chapter. Suffice it to say that there are two major properties; surface area and electronic charge.
What do we mean by surface area? As explained above the smaller the particle gets the greater
the surface area becomes. Surface area is also a function of the interior of the particle, if the
material is porous (like a sponge) then liquid or gases can travel through the interior spaces. Clay
is like a sponge; in fact with some clay a handful has as much surface area as a football field.
Fully dispersed kaolinite clay can have a surface area of 15 m
2
/g, and a bentonite close to 800
m
2
/g.

The other property is electronic charges. Think about a copper wire, how does an electric
current travel down a wire? At an atomic level there are holes where electrons can travel
through the copper atoms and areas with electron density and deficiency. When a charge is
applied to a wire, the electrons travel through these holes from a low electron density to a high
electron density.

Most surfaces have both these properties in varying degrees. These properties can influence
(catalyze) or be part of a chemical reaction. They can form a semi-permeable membrane and
channel water. They can provide pores to store atoms and bind atoms. They can also bind
together and form colloids and suspensions.

With drilling fluids these properties can influence viscosity, emulsified brine droplets, barite
particles etc. Knowledge of the nature of a surface allows for a better understanding and control
of drilling fluid properties. For example, the surface of steel usually has a net negative charge
when in an aqueous environment. When a cationic surfactant is added to the fluid, its molecules
bond to the steel, providing a defensive coating from a corrosive environment.


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2.7.2. Surface Tension
Surface tension is the force at the surface of a liquid due to adhesive forces of the liquid
molecules for the walls of the container and the attractive forces of the molecules of liquid for
each other. When the adhesive forces of the molecules for the walls of the container are greater
than the attractive forces between the liquid molecules, then the surface of a liquid confined to a
narrow diameter container will curve downward forming a concave surface called a meniscus.
Most important examples are water solutions. The water adheres to the surface of the container
greater than the water molecules are attracted to each other. We do not see this downward
curvature when the surface area is great, but if the liquid is confined to a small diameter tube
such as a graduated cylinder, pipette, burette, or volumetric flask then the surface tension is great
enough to noticeably distort the surface. In such cases when we are trying to read the liquid
surface level such as measuring a liquid in a graduated cylinder, then one should make the
reading at eye level and the lowest curvature of the meniscus should be read.
When the adhesive forces against the walls of the container are less than the intermolecular
forces, then the surface of a confined liquid will bulge upward slightly forming a convexed surface.
Again, such a surface should be read at eye level and the topmost part of the surface should be
read. Surface tension helps to explain why the feathers of a duck can help the duck float on
water.
Although molecules in a liquid are electrically neutral in nature, there are often small attractive
forces between them. These attractive forces (called Van der Waals forces) are caused by the
asymmetrical charge distribution inside the molecules. Within a body of a liquid, a molecule will
not experience a net force because the forces by the neighboring molecules all cancel out (Figure
22). However for a molecule on the surface of the liquid, there will be a net inward force since
there will be no attractive force acting from above the molecule (Figure 22). This inward net force
causes the molecules on the surface to contract and to resist being stretched or broken. Thus the
surface is under tension and has Surface tension.
Figure 22
Figure 23
mg
F
F


Due to the surface tension, small objects will "float" on the surface of a fluid. A needle will float on
water! This can be seen in Figure 23. When an object is on the surface of the fluid, the surface
under tension will behave like an elastic membrane. There will be a small depression on the
surface of the water. The vertical components of the forces by the molecules on the object will
balance out the weight of the object. Surface tension also occurs at the interface between a solid
and gas, a solid and a liquid and between two immiscible liquids.

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This is why water forms beads and soap forms bubbles. The degree of polarization in a liquid,
determines the degree of imbalanced attractive forces in it. This net force is called the fluids
surface energy. Surface tension is measured in dynes/cm. At 20C the surface tension of water is
72.7 dynes/cm, decreasing to 67.9 dynes/cm at 50C.


2.7.3 Emulsion and Foam

An emulsion is a stable mixture of two or more immiscible liquids held in suspension by small
concentrations of substances called emulsifiers. As a drilling fluid term, the word emulsion applies
to small oil drops, the dispersed or discontinuous phase, in water the continuous phase. Invert
emulsions employ oil as the continuous phase, while water is the dispersed phase. In an invert
emulsion system, the emulsified water drops may at times be sub-micron size. This creates a
proportionately large surface area.

-
O
3
SO
An Emulsifier
-O3SO -O3SO
-O3SO
-O3SO
-O3SO -O3SO
-O3SO
-O3SO -O3SO
-O3SO
Oil
Oil
H
2
O
Hydrophobic tail, "oil lover"
Hydrophilic Head
"water lover"
A water in oil emulsion



Normally the interfacial tension between oil and water is high, the two phases separate when
agitation ceases. This occurs so as to minimize the interfacial area. Emulsifiers lower the
interfacial tensions such that one phase may remain dispersed in another without mechanical
agitation.

Emulsifiers work by two mechanisms.
1. The first involves the reduction of surface tension at the dispersed phase interface. This
occurs because the molecules have a dual solubility property (hydrophilic and hydrophobic
head or tails). The second involves the adhesion to and the coating of the dispersed phase,
to prevent coalescence.
2. The second mechanism also promotes the oil wetting of and subsequent reduction in
reactivity of solid phases including steel and rock. One important fact to remember with
emulsifiers is that like is attracted to like, so in the case of oil wetting barite, a hydrophilic
head will surround the barite while the hydrophobic tail works to hold the barite in the oil
phase.
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Foams are similar to emulsions in that they have two phases; one dispersed, usually air and one
continuous. In a mist, the water is the dispersed phase. Foams and mists are colloidal systems
where the reduction of surface tension by the addition of surfactants is essential
6
. Foams are
used to help remove formation water when air drilling, clean solids from the well bore when
completing or working over wells in depleted reservoirs and as an insulating medium in Arctic
wells.


2.7.4 Surface Charges

Many of the surfaces of the various phases and components of drilling fluids are electrically
charged. The origin of these charges can be attributed to several mechanisms. The nature and
strength of the charges is dependant on these mechanisms and the nature of the environment
(fluid) the components are in.

Dislocations are variations or defects from the perfect order or symmetry in a crystal lattice.
Dislocations may involve a missing atom or hole, an atom from a different element, a complete
extra plane of atoms, or a shift of one or more lattice units relative to the lattice plane of its
neighbor. The result may be an impartation of new properties to the crystal. These might affect
hardness, conductivity and surface charge.

The substitution of ions of different valency within a crystal lattice generates charge
deficiencies within the crystal which may be manifested as surface charges. This commonly
occurs in the clay minerals used in drilling fluids.





A broken crystal lattice often introduces new surface charges to the system. This effect is readily
seen as the pH dependant edge charges on clays. The effect is also manifested with other ionic
crystals such as barite. The surface charges on barite crystals cause suspensions to become
increasingly thixotropic as the barite particle size is reduced that is, the surface area is increased.
A suspension with 100 kg/m
3
of barite might have flat gel strengths if the average particle size is
50 m. If the D
50
is reduced to 4 m the fluid might not be pumpable. The molecular water
orientation around a barite particle creates a repulsion regime similar (though smaller) to that of
clays. This is why when enough barite is added to water it remains in suspension without
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viscosifiers. Recall that both caustic and SAPP are added to barite plugs to decrease settling
time.



The dissociation of functional surface groups is the mechanism for determining the surface
charge of oxides. When ions dissociate from polymer molecules, the surface charge may change,
changing the behavior of the polymers. An example is the dissociation of Na
+
from the COOH
-

group on CMC. When this occurs the molecule retains a net anionic character, enabling it to
elongate.

Adsorption means the congregation of and adherence of the atoms, ions or molecules of a gas
or liquid to the surface of another substance, called the adsorbent. This definition describes the
processes whereby the majority of adjustments to drilling fluid properties are attained. These
include ions and water being adsorbed onto clay surfaces, polymers and clays adsorbing onto
each other, emulsifiers adsorbing onto brine droplets or surfactants adsorbing onto steel. In
solutions the adsorption process is normally accompanied by desorption of the original water.
The adsorbed species may also exchange with a previously adsorbed species.

The adsorption of a polymer molecule onto a clay surface displaces several water molecules,
increasing the free water available to the system, a favorable reaction. However, the adsorption
of ions onto clay surfaces best exemplifies the influence of the effect of adsorption on fluid
properties.

Because the surfaces of clays are electrically charged, a double layer of oriented water molecules
surrounds each clay platelet. The closest layer, the bound layer is tied to, and moves with the
clay. The outside layer, the diffuse layer has more freedom. The zeta potential is the electric
potential in the double layer at the particle/liquid interface. The double layer causes plates to
repel. However, the presence of cations reduces the size of the double layer, reducing the zeta
potential. This lowers the repulsive forces between particles. When attractive forces predominate,
particle associations increase causing an increase in viscosity. The degree to which the zeta
potential is reduced depends on the valence of the added cation, especially if low valence ions
are replaced by higher valence ions. The ratio of the comparative effect is 1, 10 or 500 for
monovalent, divalent and trivalent ions respectively. The ability to manipulate the zeta potential is
essential to control the properties of all colloidal clay systems.

As drilled cuttings enter a drilling fluid system, their surfaces invariably adsorb components of the
fluid. These include water, ions, molecules, especially hydroxyl groups, polymers and surfactants.
In order to retain consistent fluid properties, these materials must be replaced continuously.
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2.7.5 Other Surface Phenomena

Wettability is the term used to describe the tendency of a fluid to spread out evenly on the
surface of a solid. The degree of wettability is dependant on the surface tension of both the solid
and the liquid. Mercury beads up and does not wet glass because the surface tension of mercury
is too high. Water does not wet Teflon because the surface tension of Teflon is too low.
Preferential wettability describes a system of two immiscible liquids and a solid, where one liquid
preferentially wets the solid.

Adhesion refers to the state in which two surfaces are held together by interfacial forces. These
forces may consist of valence forces or interlocking action or both. A liquid will adhere to a solid if
the attraction of its molecules to the solid surface is greater than their mutual attraction. Solids
can also adhere, if they are capable of being bonded by force. When two pieces of white-hot iron
are hammered together, they become welded they adhere. The same mechanism causes sticky
drilled solids to adhere to each other and the bit and drill string, when they are forced into intimate
contact by the weight of the drill string.

Friction is a resistance that is encountered when two surfaces slide or intend to slide past each
other. There is a distinction between dry, mixed and fluid friction and also between static and
kinetic friction. The friction between moving fluid layer interfaces or between the fluid and the
surface of the pipe is often measured in pressure units. The friction between the pipe surface and
the borehole is measured as rotary torque and hole drag. On deviated wells, rotary torque and
hole drag can become excessive enough to warrant the addition of friction reducing additives.

Catalysis, one of the most important occurrences in nature, refers to the lowering of the energy
required to break (or form) a chemical bond between two atoms. The catalyst works by bringing
the atoms of a bond to be broken (or formed) into close proximity of another atom which will make
or break the selected bond. The electronic configuration of the surface molecules of a catalyst
contributes to its working mechanisms. Reactants may bond at the surface of a solid catalyst.
This is known as chemisorption. It results in changing the nature of the chemisorbed molecules
and the catalyst. Catalysts are very specific they only react to break (or form) certain types of
bonds.


2.7.6 Semipermeable Membranes and Osmotic Pressure

Osmosis occurs when there are different concentrations of a solvent on either side of a
semipermeable membrane. In order for osmosis to occur, the membrane must be permeable to
the solvent in question but not to the solute (selective membrane). Osmosis tends to equalize the
concentrations of the solvent on either side of the membrane. If the solution on one side of the
membrane is pure solvent and the membrane is impermeable to the solute, the concentrations on
either side of the membrane can never be equal. However, at a certain point, the pressure of the
solution against the membrane will prevent any further flow from the side with the pure solvent.
The pressure at this point is called the osmotic pressure.

A semipermeable membrane is a micro-porous structure which acts as a filter in the range of
molecular dimensions. Thus it allows the passage of ions, solvents and very small particles. It is
impermeable to macro molecules, such as proteins and polymers and solute species such as
colloidal materials. Figure 24 shows a semipermeable membrane separating an NaCl solution
and a solvent, water. Under atmosphere pressure, more solvent molecules pass through the
membrane in the direction of the NaCl solution than in the reverse direction. Thus the solution
becomes continuously more dilute. This means the vapor pressure of the pure solvent is greater
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than the atmospheric pressure above the NaCl solution. For the two phases to be in equilibrium
the vapor pressure must be the same in each solution.

Fig. 24:
Before
Atmospheric Pressure
Na
+
Cl
-
Cl
-
Na
+
Semipermeable membrane
H
2
O
H
2
O
H
2
O
After
After
Vapor
pressure


The vapor pressure of the solution may be raised by increasing the pressure above the NaCl
solution but not above the water. The amount of excess pressure required reaching a point of
equilibrium where there is no passage of solvent through the membrane is called the osmotic
pressure. Osmotic pressure is not exerted by solute molecules. It is a pressure that must be
applied to the ionized solution to achieve equilibrium with the pure solute.

The term water activity (A
w
) is used to describe the tendency of water vapor to move from an
area of low salt concentration to a high concentration. In the case of invert emulsion fluids, the
passage of water vapor from the emulsified water droplet into the formation or vice versa is
dependant upon the osmotic pressure differential between the brine phase and the formation
water. This phenomenon is an extremely important consideration when formulating and
maintaining invert emulsion fluids.



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2.7.7 Altering Surface Chemistry

The essence of effective drilling fluid formulation and management relies heavily on the ability to
control the behavior of individual components, through the manipulation of their surface
chemistry. When the chemistry on the surface of a component is altered, the way it interacts with
other components changes. One or many properties of the fluid may change as a result. Surface
active agents are called surfactants. They include emulsifiers, many polymers, foamers and
soaps. They are usually polymers or long chain molecules, although an ion which alters surface
chemistry could be correctly called a surface active agent. The following examples are included to
help in understanding the scope of this paragraph.

Emulsifiers act on the surface of emulsified brine droplets, lowering surface tension. They
change the preferential wettability of solids such that they become oil wet or water wet.

Clay surfaces are altered by polymers in several ways. Encapsulators reduce clay hydratability
by bonding to the clay. Deflocculants seek out positive edge sights on clays, eliminating their
effect. Flocculants act as a bridge between clay surfaces, increasing viscosity. Most polymers
reduce drill string function losses.

Foamers and defoamers both act directly on surfaces and interfaces. Some surfactants are
designed to lower clay adhesion to drilling tool surfaces. Others bond to steel tools and pipe
surfaces to protect them from corrosive environments, while still others effectively reduce rotary
torque and hole drag. Surfactants are used to control the wettability characteristics of the pore
throat surfaces in production zones. Ionic species are often added to drilling fluids to alter the
surface chemistry of its components. Various cations are used as flocculants or shale stabilizers,
while anions are often used as deflocculants.

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REFERENCES

1. Stephen Hawkings, A Brief History of Time (New York: Bantom Books, 1988), 65.
2. G. Hawley (Revised By), The Condensed Chemical Dictionary, 10
th
ed. (New York: Van
Nostrand Reinhold Inc., 1981), 788.
3. John M. Hunt, Petroleum Geo Chemistry and Geology (San Fransisco: W.H. Freeman
and Company, 1979), 208-212.
4. H. Van Olphen, An Introduction to Clay Colloid Chemistry, 2
nd
Ed. (New York: John
Wiley & Sons, 1977). 23.
5. Fred W. Billmyer, Jr., Textbook of Polymer Science, 2
nd
ed. (New York: Wiley -
Interscience, 1971), 23.
6. Darley and Gray, Composition and Properties, 336.

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CHAPTER 3

GEOLOGY


3.1 SEDIMENTRY FORMATIONS
3.1.1 Sediments and How They are Formed
3.1.2 Common Sedimentary Rocks


3.2 THE GEOSTRATIC GRADIENT
3.2.1 Normal Pore Pressure Gradients
3.2.2 Abnormal Pore Pressure Gradients
3.2.3 Subnormal Pore Pressure Gradients



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3.1 SEDIMENTRY FORMATIONS

3.1.1 Sediments and How They are Formed

Geologists categorize rocks into three main groups: igneous, metamorphic and sedimentary.
Igneous rocks are formed from the solidification of magma, molten rock, which is mainly silica,
sometimes containing dissolved gasses and solid minerals. Metamorphic rocks are produced
by the transformation of pre-existing rock into texturally or mineralogically distinct new rock. This
transformation is caused by heat or pressure or both, but without the rock melting in the process.
Most hydrocarbons are found in the third type - sedimentary rocks, therefore most drilling takes
place through sedimentary formations.

Sediment is the collective name for solid particles that originate either from the erosion of pre-
existing rocks or from chemical precipitation from solution, including secretion from organisms.
Three fourths of the surface of the continents is covered with a layer of sedimentary rock.
Sediments can be classified by size; from gravel to sand to silt to clay. (Clay in this sense refers
to size only - thus quartz can be "clay sized").

Sediment grains are often moved by water in the form of rivers, rain, waves or glaciers.
Rounding and sorting of grains occurs during transportation. Deposition occurs when the
transported material comes to rest and settles. Successive layers of sediments are usually
deposited on top of each other. Layers are called beds and may vary in consistency or
composition. They are deposited horizontally.

Lithification is the term given to a group of processes that convert loose sediment to
sedimentary rock. These include compaction (consolidation), cementation, or crystallization.
Often consolidation is imperfect and pore spaces are left between the grains. When water flows
through these spaces, precipitates often from a cementing matrix. A sedimentary rock consisting
of grains bound by cement into a ridged framework is said to have a clastic texture. Sedimentary
rocks, which develop by precipitation and the growth of crystals, are said to have a crystalline
texture. Crystalline rocks lack both cement and pore space.

Three categories of sedimentary rocks exist: organic, chemical and clastic. Commercial
hydrocarbons are almost always located in the latter two types.

Organic sediments such as coal accumulate from the remains of organisms such as plant
remains.

Chemical sediments include evaporates and carbonates. Evaporate rocks are formed from
crystals that precipitate when seawater or saline lakes evaporate. Gypsum (CaSO
4
) and rock salt
(NaCl) are examples. Usually seawater has a fairly consistent composition. The chapter on
Water-Based Fluids has a table showing the typical composition of seawater. When seawater
evaporates the various salts precipitate out in a specific order determined by their solubility after
the following fashion:

1. Carbonates - CaCO
3

Dolomite - CaMg (CO
3
)
2


2. Gypsum - CaSO
4
2H
2
O
Anhydrite - CaSO
4


3. Halite - NaCl

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4. Carnallite - KMgCl
3
6H
2
O
Potash - KCl
Polyhalite - K
2
Ca
2
Mg(SO
4
)
4
2H
2
O

Note that only the fourth stage contains extremely soluble magnesium and potassium salts. This
stage of evaporation is seldom reached. If it is, new influxes of sea water often wash these salts
away and the cycle begins again with the precipitation of carbonates and gypsum. The North
Sea's Zechstein Formation is an example of a "complex evaporate". containing various
combinations of all the precipitates listed above.

Carbonate rocks can be formed from organism induced, or inorganic chemical precipitation, or
by the cementation of accumulated shell fragments. Limestone (mostly CaCO
3
) and dolomite
(CaMg(CO
3
)
2
) are examples. Limestones made from shell; algae or coral fragments are called
bioclastic. These can also be called an organic rock.
1
Although hydrocarbon reservoirs are more
abundant in sandstone formations, the majority of the world's hydrocarbon production is from
carbonate reservoirs. This is due to the number of large carbonate reservoirs in the Middle East.
2


Most sedimentary rocks are clastic sedimentary rocks. These are formed from cemented
fragments of pre-existing rocks. In most cases they have been eroded and transported before
being deposited. Clastic rocks are often classified by their grain size. Conglomerate is a coarse-
grained rock formed by the cementation of rounded gravel. Breccia is similar, but the grains are
more angular. Sandstone is a medium-grained sedimentary rock formed by the Lithification of
sand grains. Often clay and silt occupy part of the matrix between the grains. Fine-grained rocks
are called shale, siltstone and mudstone. They typically undergo pronounced consolidation as
they lithify, although consolidation itself doesn't usually convert sediment into sedimentary rock.
Clastic formations composed of sand and silt are called arenaceous, while those composed of
clays or clay-silt mixtures are called arigillaceous. While drilling, it is possible to encounter clastic
rocks in various stages of consolidation, including the clay minerals discussed in the Clay
Chemistry chapter.

Consolidation is analogous to a pile of wet sponges where the weight of the sponges above
drives the water out of the sponge below, with most of the water being squeezed from the bottom
sponge. The model assumes that the water is free to escape or drain away. As a consequence,
the water content decreases and the bulk density of the matrix increases with depth of burial.
Figure 9.1 shows a theoretical curve of how the formation density can change with depth
assuming free drainage.

When first deposited, clastic sediments are soft and contain large amounts of water.
Consolidation is reversible at this stage and shallow sediments can be easily re-dispersed into
individual grains. These are called unconsolidated formations. However, as the sediment
becomes more compressed, the particles are brought closer to each other and the pressure
between the mineral grains or the intergranular stress begins to increase. These sediments
usually contain enough water to retain a plastic character. Plastic in this sense means that they
are capable of deformation without rupture.

Further changes, described as diagenesis (see chapter 4) can take place as the sediment ages
and the chemical and physical environment changes. This may involve increased pressure,
increased temperature and changes in pore fluid composition. For example, under suitable
conditions, montmorillonite can lose silica and water and take up potassium to form the more
stable mineral illite.

These influences can change the mineralogy of clays. Siliceous or calcareous formation water
creates silica or calcium carbonate, which bonds the minerals together. Inter-crystalline bonding
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increases the strength of the rocks and makes them more brittle. Sedimentary formations
generally become harder and stronger with depth of burial.

Complete consolidation isn't necessarily the end of the process. The discourse of the earth's
crust is on-going and various influences can alter sedimentary rocks, especially structurally. The
most notable is the upheaval and deformation caused by tectonic forces. These can result in
steeply inclined or dipped bedding planes.


3.1.2 Common Sedimentary Rocks

Some common reservoir rocks are listed below. They are typically characterized by having a
solid rock matrix and a void space or pore volume. Important properties of these rocks include
porosity, permeability, fluid saturation and bulk density.

Sandstones are made up of quartz grains with some feldspar or igneous rock fragments present.
These grains are compacted into cemented sand masses and are held together with calcite,
silica, iron oxide or various types of clays.

Shales are compacted clays and can contain quartz grains, calcium carbonate or organic matter.

Breccia is made up of fracture bits of other rocks cemented together and are common along fault
zones.

Conglomerate is a type of breccia although made up of more rounded, granular pieces of rock.
Typically found farther away from breccia and exposed to more wearing forces.

Limestone is composed of calcium carbonates, originating from seawater or shells and skeletons
of plants and animals.

Dolomite is a limestone with some of the calcium replaced by magnesium.

Chalk is a type of limestone composed of cemented shells and small fragments.

Marl is a mix of limestone 35-65% and shale.

Reef is another limestone composed primarily of corals and other marine life.

Chert is a rock composed of a dense, hard and compacted form of silica.


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3.2 THE GEOSTATIC GRADIENT

The term gradient refers to the rate of change in a given pressure value, with depth. The weight
of the combined mass of the formation rock and pore fluids is referred to as the bulk density of
the formation. Most of the sedimentary rock, which we drill through, has a specific gravity in the
order of 2.6 g/cm
3
. A tight formation, or one with limited porosity might have a bulk density of
close to this value. A young, wet formation, or an oil or gas bearing one could have a bulk
density of 2.0 g/cm
3
or less. Knowing the formation bulk density helps predict under or over-
pressured zones. It is also an input into solids control and hole cleaning efficiency calculations.
Shale bulk density is directly related to shale resistivity and to a function of shale transit time
(sonic log). A plot of either of these may reveal anomalies in bulk density.

Figure 3.1 A bulk Density Curve for a
Normally Consolidated Formation
0
1000
2000
3000
4000
1 2 2.2 2.4 2.6 3
Bulk Density
D
e
p
t
h

(
M
)



The mass of rock and pore fluid creates a geostatic pressure, sometimes called the overburden
load or stress, S. This may be expressed as equation

S = ?
b
d

Where, ?
b
is the bulk density and d is depth. The geostatic or overburden gradient is then
defined by equation 9.2:

Geostatic gradient = S
d


Normal geostatic gradients range from 2.0 to 2.5 kPa/m. Figure 3.1 illustrates that the bulk
density isn't necessarily a linear function of depth. Thus the above equations can only be used
over short sections and the stress or gradient integrated for the whole section. The relationship
between depth of burial and overburden stress is given in Figure 3.2.

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Figure 3.2 Composite Overburden Stress, s, for a
noramlly Compacted Formation
0
1000
2000
3000
4000
5000
6000
7000
0.19 0.2 0.21 0.22 0.23 0.24
Kg/cm2/m
D
e
p
t
h



3.2.1 Normal Pressure Gradients

When the sediment has compacted sufficiently for grain-to-grain contact to be established, the
overburden load or stress, S, is supported by both the mineral grains and the fluid in the
remaining spaces. The relationship is expressed in equation 9.3:

S = s + P
p


where s represents the intergranular or matrix stress and P
p
represents the pore pressure.
Normally, where the formation is freely drained and the pore spaces are interconnected, P
p
is
given by equation 9.4:

P
p
= f d

where f is the pore density and d is the depth. The actual gradient should be calculated by:


f
Gradient = d .00981

where the gradient is in kPa/cm and d is kg/m
3
.

The density of the pore fluid is mainly dependent on the salinity as water is essentially
incompressible. A variation in pressure gradient can result from a reduction in fluid density with
depth as the formation temperature increases. Formation pore pressure gradients are typically in
the range from 9.8 to 11.5 kPa/m.


3.2.2 Abnormal Pore Pressure Gradients

The preceding description of the pressure regime varying smoothly with depth isn't always
encountered. Abnormal pressures occur when fluids expelled by compacting sediments cannot
migrate freely to the surface. One of the most important data inputs required for designing casing
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and drilling fluid programs is the pore pressure profile. There are a number of causes of this
anomalous behavior.

In argillaceous, mainly clay formations, water might not escape during the drainage stage. That
is, the rate of expulsion is unable to keep pace with the rate of compaction. Shale formations
having high concentrations of clay may have permeabilities approaching 10
-6
millidarcies, so
water drainage is very slow.

The presence of montmorillonite can compound the problem further. It has been established
beyond doubt that geo-pressures found in the Gulf Coast at depths of 3 000 m are associated
with diagensis.
3
This relates to the expulsion of water when montmorillonite is transformed to
illite. There is also a definite correlation between formation Bentonite content and abnormal
pressures in some areas of the North Sea. On the other hand, aranaceous-sandy-formations,
which arent capped by an impervious formation, may have permeabilities in the range of 1 to 10
3

mullidarcies, and thus drain quite readily.

In over-pressured formations, sometimes called geo-pressured formations, the analogy made to
the wet sponges now has some of the sponges wrapped in plastic so the water can't escape. In
this situation the weight of the other sponges is born mainly by the fluid rather than the solid
phase.

Geo-pressured formations may be encountered at fairly shallow depths in several areas of the
world. Included are the North Sea's Forties Field, the Beaufort Sea's Amauligak Field and the
Gulf Coast. Figure 3.3 shows how a variance from a normal bulk density curve indicates the
presence of shallow geo-pressure at a North Sea location. Extremely high geo-pressures are
only found at considerable depth. These are often associated with diagenesis, especially in Gulf
Coast Wells below 3,000 m.

Tectonic activity may initiate the disturbance of normally pressured formations by faulting, lateral
sliding, folding or intrusion. These movements can place a formation out of equilibrium with the
normal pressure regime. If migrating interstitial fluids are sealed, by impermeable formations
such as shales, the pressure regime can eventually become abnormal.

Salt is also impermeable to migrating fluids and can easily dissolve and then re-crystallize in a
different shape. Thus formations directly under a salt formation often have abnormally high pore
pressures because fluids trying to escape as a result of consolidation are unable to. Further, if
the salt is forced into a dome it may exert abnormal stresses on adjacent formations.

The abnormal conditions should be as closely defined as possible by careful interpretation of
seismic or offset well data. Wells that are close to each other may have quite different pressure
profiles. They often require separate drilling programs due to details such as whether they are
drilling up or down dip to a folded formation or near to a salt dome.

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3.2.3 Subnormal Pore Pressure Gradients

The pore pressure gradient can also be less than that of fresh water. This occurs in producing
gas formations where production has drawn-down the original pore pressure. Or, the interstitial
fluid may have migrated previously, leaving void pores with zero pressure. In both cases, the
remaining rock matrix must now support more or all of the overburden stress. If the overburden
stress exceeds the strength of the matrix - its yield stress value - the matrix will fail and the
ground at surface or the seabed can actually sink. This is called subsidence. The most notable
occurrence of such a phenomena is in the North Sea's Ekofisk field.

When penetrating or completing in formations with subnormal gradients, the volume of fluid lost to
the formation is usually high. Special precautions, such as the addition of bridging solids may
have to be included in the Fluids program to minimize fluid-induced formation damage.
Occasionally full circulation returns can't be established regardless of the number of golf-balls and
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tons of cement pumped down the wellbore. In some areas operators drill blind or without returns
through these formations.

A situation where two different pore pressure gradients exist in the same interval of open hole can
be difficult at best. A rapid transition to overpressure can cause blowouts while drilling. If the
combination of shut in casing pressure and fluid hydrostatic pressure exceeds the matrix strength
or the pore pressure of the formation above, loss of fluid and even wellbore fracturing can occur.
In this case a good indication of pressures and volumes is unattainable and the result could be an
underground blowout. If the escaping, pressurized pore fluid fractures the formation to the
surface, loss of ground integrity can and has caused rigs to sink out of sight.

In some areas, such as the Beaufort Sea, pore pressure reversals are encountered. Here a
column of drilling fluid may be lost when the bit penetrates a formation having a lower pore
pressure.
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REFERENCES

1 Charles C. Plummer, David McGeary, Physical Geology, 4th ed. (Dubuque, IOWA: Wm.
C. BORWN PUBLISHERS, 1988).120.

2 Allen and Roberts, Production Operations, Vol 1, 3.

3 Darley and Gray, Composition and Properties, 349.

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CHAPTER 4

CLAY CHEMISTRY AND PROPERTIES

4.1 KEY POINTS AND SUMMARY

4.2 THE ORIGIN AND BASIC STRUCTURES OF CLAY MINERALS
4.2.1 The Chemical Weathering of Feldspar
4.2.2 Building Units
4.2.3 Isomorphous Substitution
4.2.4 Associated Cations
4.2.5 Broken Edge Charges

4.3 DESCRIPTIONS OF COMMON CLAY MINERALS
4.3.1 Kaolinite
4.3.2 Illite
4.3.3 Smectites
4.3.4 Chlorite
4.3.5 Mixed Layer Clays
4.3.6 Attapulgite and Sepiolite

4.4 FORCES BETWEEN CLAY PARTICLES
4.4.1 Attractive Forces
4.4.2 Repulsive Forces

4.5 THE BEHAVIOUR OF CLAYS IN DRILLING FLUIDS
4.5.1 Dispersion
4.5.2 Flocculation
4.5.3 Aggregation
4.5.4 Deflocculation
4.5.5 Viscosity in Water-based Systems
4.5.6 Viscosity in Oil-based Systems
4.5.7 Gelation

4.6 FORMATION CLAYS
4.6.1 Diagenesis
4.6.2 Sediments
4.6.3 Clay Analysis
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4.1 KEY POINTS AND SUMMARY

Clay minerals almost always constitute a percentage of the solid phase of drilling fluids. They
may be added intentionally to control certain properties, or they may become entrained in the fluid
while drilling through formations containing clays.

Clay minerals are crystals. They are formed through the weathering process, or alteration of
parent minerals such as feldspar. Most clay minerals are plate-like in shape. Each Platelet is
composed of many repeating unit layers, stacked on top of each other. Unit layers are thin and
flat. Each unit layer is composed of two or more sheets.



There are two different types of sheets which can combine to form unit layers. They are named
after their geometric shape, or tetrahedral and octahedral sheets. Often there are variances in the
chemical composition of these sheets. These chemical variances and the order, in which the
sheets are stacked to form unit layers, impart various properties to different clay minerals.

C
H H
H
H
Tetrahedral methane
Cl
P
Cl
Cl Cl
Cl Cl
Octahedral phosphorus hexachloride


Frequently the chemical variations in the composite sheets cause charge deficiencies within
individual unit layers. This usually results in an overall negative charge on the flat surface of a unit
layer. Charges also exist on the broken edges of clay minerals. In a suspension these broken
edge charges are influenced by the pH.



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Common clays include kaolinite, illite, smectite and chlorite. Bentonite is a variety of smectite
the most common clay in the drilling fluid industry. This chapter examines the structural and
behavioral differences of the most common clay minerals.

The properties which clays impart to suspensions depend partly on how individual clay platelets
interact both with each other and the fluid. The balance between attractive forces and repulsive
forces between clay plates is the most important factor governing the physical properties of clay
suspensions.

Most clays have an affinity for water and some may swell when they become water wet. The
selection of a drilling fluid is often related to the reactions between the clay or shale intervals and
the drilling fluid. If not properly formulated, the drilling fluid can strongly alter the stability of these
formations, affecting the stability of the wellbore. The clays found in production sands can swell or
move when contacted by water, causing formation damage.

A basic understanding of the composition of clay minerals facilitates a better comprehension of
how and why they behave in certain environments. Once this comprehension is achieved, the
environment of a suspension may be altered to induce clays to behave beneficially.


4.2 THE ORIGIN AND BASIC STRUCTURES OF CLAY MINERALS

Clay may be described as a natural, fine grained, earthy material which develops plasticity when
moistened. Clay minerals include any group of hydrous silicates of aluminum and other metals.
They are generally classified as aluminum silicates. Clay minerals are most often formed when
sediments are deposited and compacted. Other minerals which are common in sedimentary rock
may contain a percentage of clay minerals.

X-ray diffraction and chemical analysis indicates that all clay minerals are layered and
crystalline. Chemically, they all contain large amounts of aluminum, silicon and oxygen or
hydroxyl. They may also contain smaller amounts of iron, magnesium, calcium, potassium and
sodium. It is these latter constituents which give individual clay minerals their own unique
properties. Clays may be classified according to particle size in either geological or oil field terms.

Clay crystals process some unique properties. They usually consist of wafer-like structures called
unit layers. Unit layers consist of two long axes and one short but definable axis, usually in the
order of 10 . This results in a large surface area. Unit layers process electrical charges which
exist on the broken edges, and on the flat surface of the layers.


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In clay minerals, many unit layers are repeated or stacked to constitute each clay mineral. Each
unit layer is composed of thin, flat sheets, which differ in structure. In mineralogical terms, these
individual sheets are sometimes also referred to as layers. For example, illite is sometimes called
three-layer clay because each unit layer contains three sheets. In this chapter, for the sake of
simplicity, the term sheet is used to describe the (octahedral and tetrahedral) sheets which
combine to form unit layers. The term unit layer is used to describe the layers which are stacked
to form a clay mineral.


4.2.1 The Chemical Weathering of Feldspar

Clay minerals may originate from the weathering process of a parent rock, or by other processes
such as the alteration of volcanic rock in situ. Many clay minerals originate from weathered
feldspar minerals. The weathering of the mineral feldspar is an example of how an original crystal
can be altered by weathering to form an entirely different type of crystal. When feldspar a
framework silicate reacts with the H
+
ion from H
2
CO
3
(formed from CO
2
and H
2
O) it forms clay
minerals, which are sheet silicates.

The general process may be stated:

2KAlSi
3
O
8
+ 2H
2
CO
3
+ H
2
O
H
2
O + CO
2
H
2
CO
3
Al
2
Si
2
O
5
(OH)
4
+ 2KHCO
3
+ 4SiO
2
Feldspar Clay
Silica


This process occurs when rainwater acquires carbon dioxide as it soaks into soil. The hydrogen
ion provided by the slightly acidic water reacts with the feldspar becoming incorporated into the
clay mineral. When hydrogen moves into the crystal structure, it replaces potassium from the
feldspar. The potassium ion and the original bicarbonate ion are removed by the moving water.
Some of the silicon from the feldspar is also removed. The new crystal is called a clay mineral.
This weathering process applies to K feldspar (orthoclase) forming potassium salts, and Na
feldspar and Ca feldspar (plagioclase) forming sodium and calcium salts respectively.

It should be noted that in his book, Clay Mineralogy, Ralph Grim points out that several clay
minerals have been synthesized from various mixtures of crystalline minerals and reagents at
various temperatures and pressures. This applies to some of the clays discussed in this chapter,
including kaolinite, illite and smectite. In fact kaolinite has been formed from a variety of parent
minerals including leucite. Grim states: "An acid rock containing considerable quantities of
potassium as well as magnesium will yield illite and smectite. If the content of magnesium is
low, illite will be the only product, and if the content of potassium is low, smectite will be the only
product. Rapid removal of the potassium and magnesium leads to the formation of kaolinite". The
resultant clay minerals are often transported and deposited as sediments. Sedimentation is a
geological process discussed both at the end of this chapter and at the beginning of the chapter
entitled Borehole Stability.

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4.2.2 Building Units

There are only two types of the thin, flat sheets which combine to form the unit layers which
make up clay crystals. They are named after the geometric co-ordination of their constituent
atoms, or tetrahedral and octahedral sheets. The order in which sheets are stacked to form unit
layers and the methods by which they are bound together, serves to classify clay minerals. Figure
4.1 shows a simplified example of four common types of layered clay minerals.

Figure 4.1

OH OH OH
-
O
-
O
-
O
H
+
H
+
H
+
Kaolinite
Unit
layer
-
O
-
O
-
O
Illite
Unit
layer
-
O
-
O
-
O
K
+
K
+
K
+
-
O
-
O
-
O
Montmorillonite
Unit
layer
-
O
-
O
-
O
Ca
+
Ca
+
Ca
+
-
O
-
O
-
O
Chlorite
Unit
layer
-
O
-
O
-
O
=Octahedral
=Tetrahedral


Figure 4.2a denotes a single tetrahedron or four sided unit. It usually contains a silicon ion (Si
4+
);
hence it may be referred to as the silica sheet.

O
Si
O
O
O
A tetrahedral subunit (SiO
4
4-
)
fig. 4.2a


The silicon atom is located in the center of the tetrahedral an equal distance from four oxygen
atoms. In some cases the center may be empty or the silicon may be replaced by magnesium or
iron. Figure 4.2b illustrates that three of the four oxygen atoms of each tetrahedron are shared by
three neighboring tetrahedron to form a sheet of composition Si
6
O
9
(OH)
6
.
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Figure 4.2b: Side view of the tetrahedral sheet


The extent of this sheet is indefinite. The shared oxygen atoms can be seen to form a plane or
basal surface. When viewed from above (Figure 4.2c) a hexagonal void can be seen in the
network of silicon - oxygen silicon bonds.

Figure 4.2c:



Figure 4.3a shows a single octahedral or eight sided unit. It usually contains an aluminum (Al
3+
)
ion in octahedral co-ordination with 6 hydroxyl ions. In some cases the center of the octahedron
may be empty, or the aluminum may be replaced by other metals magnesium or iron.
Figure 4.3b illustrates how hydroxyls are shared between individual octahedron, as they combine
to form sheets. The area extent of octahedral sheets is also indefinite.

The octahedral sheet usually has a balanced charge structure. When the octahedral metal ions
are aluminum (trivalent), only two out of every three center sites can be filled. In this case the
sheet is termed dioctahedral. Its composition is Al
2
(OH)
6
the mineral gibbsite. When the metal
atoms are magnesium (divalent) all the spaces are filled to balance the charge structure and the
sheet is termed trioctahedral. In this case the composition is Mg
3
(OH)
6
, the mineral brucite.

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Figure 4.3:



The tetrahedral and octahedral sheets have dimensions such that they may be bonded by
sharing common oxygen atoms. Figure 4.7 shows an example of a single tetrahedral sheet bound
to a single octahedral sheet forming a unit layer two sheets thick. This is the mineral kaolinite.
Note how the apex of each tetrahedron points toward the octahedral sheet. The oxygens at these
apices displace two out of three hydroxyls originally present on the octahedral sheet. This forms a
bond of common oxygen atoms between sheets, creating the unit layer. In the case of two sheet
clay, there is an oxygen network on one basal surface and a hydroxyl network on the other.

When three sheets combine to form one repeating unit, an octahedral sheet is always located
between two tetrahedral sheets. Again, tetrahedron apices point towards the octahedral sheet.
Two thirds of the octahedral hydroxyls are displaced and common oxygen atoms are shared
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between sheets. In this case, both basal surfaces of the layer consist of an oxygen network.
Figure 4.8 shows how illite is formed from this type of three-sheet layer.

Tetrahedral (silica) and octahedral (aluminum) sheets combine naturally to form unit layers. The
bonding between sheets is covalent, helping to stabilize charges in the unit layer. The ratio of
tetrahedral to octahedral sheets can be 1:1, 2:1 or 2:1:1 in a given unit layer. When the unit layers
are stacked together they form a structure called the crystal lattice.
1
The distance between a
plane in a unit layer and the corresponding plane in the next unit layer is called the c-spacing or
basal spacing (see Figure 4.4). This distance is about 9 in three-layer minerals and 7 in two
layer minerals. The unit layers are held together by van der Waals forces and secondary
valences between adjacent atoms.
2
The lattice tends to cleave between the exposed basal
surfaces. The structure of the four clay minerals encountered most frequently in the drilling
industry is shown in Figures 4.7, 4.8, 4.9 and 4.12.

Figure 4.4: An expanding lattice





4.2.3 Isomorphous Substitution

The octahedral and tetrahedral sheets as described are in perfect charge balance. However the
ions occupying the center sites may be replaced by ions of similar or lower charge. For example,
the tetrahedral silicon atom may be replaced by aluminum or iron. These ions have the same co-
ordination dimensions but cannot accept all of the electrons donated by the surrounding four
oxygen atoms. This substitution creates a surplus of electrons and a negative charge within the
clay structure. This is termed a charge deficiency and is in fact the distinction between clay
minerals and some other types of minerals including the smectite prototypes (see 4.3.3).
Similarly, magnesium or iron may replace aluminum and create a negative charge in the
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octahedral sheet. This structural feature, where silicon or aluminum ions are replaced is called
isomorphous substitution or like ion replacement. It usually creates negative charges in the
sheet. These charges do not vary with pH.

Different clay minerals are characterized by different patterns of isomorphous substitution, giving
that mineral its own characteristics. The two variables are the extent and the position of
substitution.


4.2.4 Associated Cations and Cation Exchange Capacity (CEC)

The negative charges created by isomorphous substitution are usually countered by the close
association of a cation on the basal surfaces of unit layers. The nature of the cations hydration
energy has a significant influence on the structure of the clay and its properties.

Table 4.1: Diameters of Cations in the Dehydrated and Hydrated Form

Ion
Dehydrated ion
diameter ()
Charge Density
(charge/
2
)
Hydrated ion
diameter ()
Sodium (Na
+
) 1.90 0.088 5.5 11.2
Potassium (K
+
) 2.66 0.045 4.64 7.6
Magnesium (Mg
+2
) 1.30 0.376 21.6
Calcium (Ca
+2
) 1.90 0.176 19.0


The extent of the interaction of water with the charged ion depends on the charge density of the
ion. Different ions have a range of sizes depending on the number of electrons in the atom. The
sizes of dehydrated cations are given in Table 4.1. The charge density is the charge on the ion
divided by the surface area. This has been calculated for the common ions. Tightly associated
water forms layers around the cation, as illustrated in Figure 4.5.

Magnesium has the highest charge density and forms the largest hydrated ion.
The other divalent ion, calcium, also forms a large hydrated ion with a high charge
density.
Sodium forms an intermediately hydrated ion.
Potassium forms a weak complex.

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Figure 4.5: Orientation of water molecules near a cation



This shows that there are large differences between the energy of hydration of the commonly
occurring ions. These differences in cationic hydration energy are important when considering the
hydration energy of clays with different exchanged cations.

Cations usually associate in the crystal lattice at the site nearest the excess electrons resulting
from isomorphous substitution. The nature of the association between the cation and this site
depends on several factors. These include:
The nature of the isomorphous substitution site;
The type of cation;
The relative concentrations of competing cations.

Higher valency ions are usually adsorbed preferentially. A study by S.B. Hendricks et al in 1940
suggested that the order of preference or the replacing power is usually:

H
+
> Ba
++
> Sr
++
> Ca
++
> Cs
+
> Rb
+
> K
+
> Na
+
> Li
+


This order may vary between types of clay and concentrations of cations. The fact that hydrogen
is so strongly adsorbed makes cation exchange pH dependant.

The ability of clay to absorb cations is termed its cation exchange capacity or CEC. It is
expressed in milli-equivalents of the cationic dye methylene blue absorbed by each one hundred
grams of dry clay (meq/100g).
In some clay such as montmorillonite and illite, the majority of the exchange sites are located on
the basal surfaces. In the case of kaolinite, the broken bonds at the edges of the crystal account
for the majority of the exchange sites. This explains the relatively low colloidal activity of kaolinite
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when compared to montmorillonite. Montmorillonite, having a higher CEC value, swells to a
greater degree, contributing to higher viscosities at lower concentrations.

A field test based on the adsorption of methylene blue, tests the approximate value of the CEC of
the whole fluid. This test does not determine cationic species. Clays also have the ability to
exchange anions, but to a much lesser degree than their cation exchange capacities.


4.2.5 Broken Edge Charges

The balanced charge structure in a clay crystal is broken when the crystal is fractured. (Broken
edge charges are generated for all fractured ionic crystals, including barite and calcium
carbonate.) A feature of clay minerals is that they are built up from weakly basic aluminum
hydroxide and weakly acidic silicic acid. The basic groups in the clay react with hydrogen ions,
and the acidic groups react with the hydroxyl ions to generate predominantly positive or negative
charges on the edges.

At neutral pH, the broken edge charges are close to equilibrium.
When alkaline conditions are created, predominantly negative edge charges are soon
established. The action of breaking clay crystals and reacting the exposed aluminum ions
with hydroxyl ions occurs continuously in drilling fluids. It is one reason why caustic soda
must be continually added to maintain a desired alkalinity. The treatment levels of caustic
can be minimized if the concentration of clay solids is kept low.
Acidic pH values are not normally used in drilling fluids, but the clays in sandstone
reservoirs may be exposed to acids during stimulation procedures. If this process alters clay
charge distributions and disturbs the clays, blockage of formation pores may result. This
phenomenon is explained in greater detail in the chapter on Production Zone Drilling,
Completion and Workover Fluids. The development of pH dependant charges on fractured
crystal edges occurs in all clay minerals.

Figure 4.6: Broken edge charges on a clay crystal


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4.3 DESCRIPTIONS OF COMMON CLAY MINERALS

4.3.1 Kaolinite (Two sheets per unit layer)

Kaolinite is two-sheet clay. That is, the unit layers consist of one octahedral sheet and one
tetrahedral sheet. The general formula for kaolinite is Al
2
Si
2
O
5
(OH)
4
, a diagrammatic sketch of the
1:1 structure of kaolinite is given in Figure 4.7.

Figure 4.7: Kaolinite structure



The sheets are bonded together in the covalent manner described in section 4.2.1. The oxygens
at the tetrahedral apices displace two out three octahedral hydroxyls. This leaves both, a
hexagonal shaped oxygen surface and a hydroxyl surface exposed on each layer. Very few if any
isomorphous substitutions occur in either sheet, resulting in balanced charges within the layer.

Unit Layers are stacked such that tetrahedral oxygens oppose octahedral hydroxyls.
Consequently strong hydrogen bonding exists between unit layers. This prevents lattice
expansion or swelling, resulting in low viscosity suspensions. Few, if any cations are adsorbed on
the basal surfaces. Kaolinite typically has CEC in the range of 3 15 meq/100g of dry clay.

The natural crystals are well ordered and do not readily disperse in water. They may consist of
about 100 unit layers in a book like structure. Charges on the platelets are usually broken edge
charges which are pH sensitive. Platelets carry a characteristic double layer of oriented water of
10 and 400 thickness respectively. Kaolinite is believed to posses the greatest tendency to
migrate when considered in the context of formation damage caused by particle migration.
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(Dickite is a type of Kaolinite found in sandstone reservoirs). Kaolinite may be transformed to
chlorite or illite with depth and age. Kaolinite is found extensively in marine deposits and shale. It
is used in the ceramics and paper making industries.


4.3.2 Illite (Three sheets per unit layer)

Illite is three-sheet clay. It may be described as mica which contains some water. The unit layers
in illite consist of an octahedral sheet located between two tetrahedral sheets. The prototype
clays are trioctahedral biotite, and dioctahedral muscovite. Figure 4.8 depicts the 2:1 structure of
muscovite. Note the location of the potassium ion. The general formula for muscovite may be
written as KAI
3
Si
3
O
10
(OH)
2
.

Figure 4.8: Illite (muscovite) structure



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The three sheets are bonded together in the familiar covalent manner described in section 4.2.1.
Unlike montmorillonite, the majority of the isomorphous substitutions in illite occur in the
tetrahedral sheet. Usually aluminum replaces silicon. If substitutions occur in the octahedral
sheet, magnesium or iron usually replaces aluminum.

Potassium is always located in the cation exchange site between unit layers. It fits neatly into the
hexagonal hole in the exposed oxygen network. Illite is common in marine sediments and it is the
presence of this potassium which causes the deflection in gamma-ray logs, indicating the
presence of shale. Unlike montmorillonite, the charge deficiency is situated in the two outside
sheets. Therefore the bond between unit layers is strong. Potassium normally cannot be
exchanged.

In degraded illite the potassium may be leached from between layers making it possible for other
cations to interact with the clay. Thus, some illite may disperse in water and hydration and cation
exchanges may occur at the surfaces of illite aggregates. This promotes some tendency to
hydration and c-spacing increase. Potassium stabilizes illite, due to the small hydrated diameter
of the potassium ion (see table 4.1). The normal CEC of illite is between 10 40 meq/100g of dry
clay.


4.3.3 Smectites (Three sheets per unit layer)

The smectite group of clays has been classified by the American Petroleum Institute (API Project
55). This classification is based on:
Their prototype mineral talic or pyrophylette;
The degree of isomorphous substitution;
The species of atoms substituted.

Familiar members of the smectite group include: talic, hectorite, vermiculite and montmorillonite.
Because of its swelling characteristics, montmorillonite is the best known and most studied of the
smectites.

Smectites are three-sheet clays. An octahedral sheet is located between two tetrahedral sheets.
Figure 4.9 depicts the 2:1 structure of sodium montmorillonite. The general formula for
montmorillonite may be written as 2[(Al
2-x
Mg
x
)Si
4
O
10
(OH)
2
] + exchange cation.

The three sheets are bonded together in the covalent manner described in section 4.2.1. Bonding
between unit layers is weak because oxygen basal surfaces oppose each other. The forces
bonding the layers are reduced further because, unlike illite, the majority of the isomorphous
substitutions and their resultant charge deficiencies occur in the octahedral or middle sheet. Here,
magnesium or iron is substituted for aluminum. Aluminum is sometimes substituted for silicon in
the tetrahedral sheet.

The net charge deficiency in montmorillonite is dependent on the degree of substitution and
varies widely. Various cations may bind the unit layers together.
3
The two types of montmorillonite
applicable to the drilling industry are calcium montmorillonite and sodium montmorillonite
(bentonite). In 1926, Ross and Shannon redefined the term bentonite to limit it to clays produced
by the alteration of volcanic ash in situ.

Under ordinary conditions, a smectite with sodium as the exchange ion frequently has one
molecular water layer, and the c-spacing is about 12 . With calcium, there are frequently two
molecular water layers.

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Because the bonding is weak, the crystal lattice cleaves easily. Since the majority of substitutions
occur in the octahedral sheet, cations occupying exchange sites between unit layers don't
completely lose their ionic character. The tetrahedral sheet prevents them from coming close
enough to the charge deficiency site. This residual ionic character creates an attraction for polar
molecules.

Figure 4.9: Smectite (montmorillonite) structure



If water is allowed to satisfy this, attraction an increase in c-spacing results. The c-spacing
increase is greatest when sodium occupies the exchange site. Sodium, being monovalent may
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only satisfy a basal surface charge deficiency of one. On the other hand, the divalent calcium ion
can satisfy a charge deficiency of two, and more readily associate with two adjacent layers. Thus,
smaller quantities of sodium montmorillonite will provide higher viscosities in suspensions.
Calcium montmorillonite can be converted to sodium montmorillonite using a process involving
sodium carbonate.

The swelling pressure of sodium montmorillonite is so strong that crystals may separate into
individual unit layers. When unit layers separate, the sodium may disassociate with the sheet
leaving a net negative charge on the face of the sheet. The charges on the broken edges of
montmorillonite vary with pH.

Dimensions of hydrated sodium montmorillonite particles have been measured using various
electro-optical techniques.
4
When single, three-sheet unit layers occur in a suspension the
hydrated radius could be as large as 230 . If a particle were enlarged to something we could
touch it might look like a coin 1 mm (0.04 inch) thick with a diameter of 25 mm (1.0 inch). In fact, if
one of gram of pure sodium montmorillonite was able to hydrate to single unit layers, the
dimensions would be about 800 m
2
.

In a drilling fluid application, one is concerned with either exploiting or nullifying the swelling
characteristics of smectites. When bentonitic formations are penetrated, their tendency to hydrate
and swell can cause problems such as mud rings, bit balling and borehole instability. Some
inhibitive fluid systems are designed around the dimensional and charge relationships between
the clays hexagonal oxygen networks and cations such as potassium, aluminum and calcium.

Bentonite is purposely added to some drilling fluid systems to improve viscosity, suspension,
lubricity and filtration characteristics. Viscosity or resistance to flow is provided by the large flat
shape of the sheets, but it is the electrostatic charges on the sheets which make bentonite
unique. These charges cause water in the vicinity of the clay plate to become structured or
crystalline. When the suspension is at rest, the plates align themselves to satisfy any inherent
charge deficiencies in the suspension. Structure is built up and resistance to flow (viscosity)
increases. When enough shear or motion is applied to the suspension to break some of this
alignment, the structure degrades. Resistance to flow then decreases and the fluid becomes
thinner (Figure 4.10).

Figure 4.10: Shear thinning: the alignment of bentonite at rest and in motion
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A shear-thinning fluid makes an ideal drilling fluid. This building and breaking of structure can be
repeated infinitely in bentonitic fluids. The thin, flat shape of bentonite particles provides most
water based systems with superior fluid loss and cake characteristics. Individual plates tend to lay
flat against any surface where a pressure differential exists (Figure 4.11).
Figure 4.11: Effect of bentonite on filtration and cake properties



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Operators usually require that the bentonite they purchase meet a certain standard such as the
API specifications (Table 4.2). Natural supplies of good quality bentonite are being depleted.
Suppliers may peptize or beneficiate bentonite with polymers to meet operator or API
specifications. Over-peptization can cause the polymers to act as a flocculant with adverse
results. Specifically, a Ben-Ex type viscosity hump may occur and the viscosity will decrease.
This has prompted both API and others to develop tests for the degree of peptization in
commercial bentonite. The results of these tests may be reported as the peptization index (see
volume II). The CEC of montmorillonite is 70 130 meq/100g of dry clay.

When bentonite is used to viscofy a non polar, oil-based fluid it must first be treated with a
cationic amine. This makes the clay hydrophobic or oil wettable (organophilic).

Table 4.2 Bentonite Requirements for API Specification (section 4)

Parameter Specification
Moisture, as shipped from point of manufacture: 10% maximum
Wet screen analysis, residue on U.S. Sieve (ASTM) no. 200: 4% maximum
*Viscometer dial reading at 600 rpm; 30 minimum
*Yield point, lb/100 ft
2
:
3 x PV Maximum
*Filtrate:
15.0 cm
3
, maximum

* Properties of a suspension of 22.5 g of bentonite (as received) in 350 cm
3
of distilled water;
stirred 20 minutes; allowed to stand overnight (16 hours); re-stirred 5 minutes before testing.

Test to be made as stated in API RP-13A, " Drilling fluids Specifications".


4.3.4 Chlorite (four sheets per layer)

Chlorites repeating unit is composed of four sheets. Figure 4.12 describes the 2:1:1 structure of
chlorite. The general formula is 2[(SiAl)
4
(MgFe)
3
O
10
(OH)
2
] + (MgAl)
6
(OH)
12


Figure 4.12: Chlorite structure
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A tri-octahedral sheet where some aluminum is replaced with magnesium is referred to as the
brucite sheet. It alternates with a three-sheet configuration similar to that seen in smectites and
illites. There is some substitution of aluminum for magnesium in the brucite sheet, giving it a net
positive charge. In the three-sheet configuration, some silicon ions are replaced by aluminum,
resulting in a net negative charge. These charges balance the structure of the unit layer and bind
the brucite sheet to the three-sheet configuration. This results in a low net charge in chlorite,
although the bonding between unit layers is strong.
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The CEC of chlorite is 10 40 meq/100g of dry clay. The reason this is higher than the CEC of
kaolinite is because in certain degraded chlorites, part of the brucite layer is missing. This permits
some degree of inter-layer hydration and lattice expansion.


4.3.5 Mixed Layer Clays

The term "mixed layer" clays is usually included in X-ray diffraction analysis. In some formations
mixed layer clays account for a fairly large percentage (greater than 10%) of the clay fraction.

Mixed layer clays often contain one or more representatives from the smectite (expanding) group.
The sequence of layers may be ordered or random. Usually these clays hydrate, cleave and
disperse to a greater extent than most other clay mineral lattices.


4.3.6 Attapulgite (salt gel) and Sepiolite (thermal gel)

Attapulgite and sepiolite may contain tetrahedral and octahedral structures. They are dissimilar
from the clays previously discussed because their overall structure does not consist of flat layers.
Instead, individual particles have a long, thin, needle-like shape. These needles occur in bundles
and are referred to as laths. Because of the shape of these clays, their use is prohibited in some
areas.

Attapulgite has a fibrous texture and a chain structure. Four silica tetrahedrons occur on either
side of the octahedral sheet with their apices directed towards the octahedral sheet. These
structural units alternate in a checker board pattern, and a series of channels is left between
them.

These channels contain "zeolitic" water, and can contain up to 4 water molecules per unit cell.
This water is strongly bound to the structure. There is a cleavage plane along the axis, parallel to
the silica chains, so that the mineral crystals have a needle-like shape, typically 1 m long and
0.01 m wide. The surface area can adsorb moderate quantities of water, contributing to
viscofying properties. These clays dont hydrate and disperse in the normal manner. The
maximum viscosity in suspensions is achieved by shearing the clays enough to degrade the
bundles into individual needles or laths. Shearing of the particles requires maximum agitation in
order to yield this clay fully.

The CEC of sepiolite is 10 35 meq/100g of dry clay.

Because both surface area and charge are relatively low, ionic species in solution have little
effect on the rheological properties of these clays. This makes them resistant to ionic
contamination causing flocculation. The smaller surface area also causes them to be more
resistant to thermal or mechanical flocculation (see Figure 4.13).
Sepiolite exhibits the best rheological properties at high temperatures.
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Figure 4.13: Differences between bentonite and sepiolite

100 C 200 C



100 C 200 C


Bentonite particles begin to aggregate or
stick together
Sepiolite needles have a small area of
inter-action

The disadvantages of attapulgite and sepiolite are, poor filtration characteristics due to their brush
heap structures and concerns regarding safety to personnel stemming from the fibrous nature of
the clay crystals.

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Table 4.3: Summarization of clay characteristics

LAYERS
OCTAHEDRAL
SHEET
EXPANSION GROUP SPECIES
Two-sheet (1:1) Dioctahedral Non-swelling Kaolinite
Kaolinite
Dickite
Narcite
Some swelling Illite Illite
Dioctahedral
Swelling Montmorillonite
Ca
+
2
Montmorillonite
Na
+
Montmorillonite
Three-sheet
(2:1)
Trioctahedral Swelling Vermiculite Vermiculite
Four-sheet
(2:1:1)
Trioctahedral Non-swelling Chlorite Chlorite varieties


4.4 FORCES BETWEEN CLAY PARTICLES

The preceding text and the review on basic chemistry both discuss the surface charges common
to most clay minerals. In both fresh and saline environments, inter-particulate attraction and
repulsion forces operate simultaneously.
The attractive forces are inherent and are not affected by salinity.
On the other hand, the repulsive forces decrease with increasing salt concentration.
In fresh water the repulsive forces dominate and the solution is stable.
In salt water, the repulsive forces are reduced to where the attractive forces dominate and
particle associations begin to form.
5

The ensuing text attempts to explain how these
mechanisms work.


4.4.1 Attractive Forces

A major attractive force between unit layers in clays are short range electrostatic forces called
Van der Waals forces. These forces are important in holding clay crystals together. Van der
Waals forces may be defined as the weak attractive forces that act on neutral atoms and
molecules. They may arise because of the polarization induced in each of the particles by the
presence of other particles. Electrons in atoms normally occupy symmetrical orbitals around the
charged nucleus. However, the symmetry may be instantaneously disturbed, setting up a dipole
or charge separation. This dipole then generates an attractive force in a neighboring atom.

These forces are weak and only operate over short distances, but they can be significant for
relatively large surfaces such as clay platelets. The relationship between attractive energy,
repulsive energy and separation distance is shown in Figure 4.14. These forces are independent
of ion concentration or type.
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Figure 4.14: Van der Waals forces dependence on distance between 2 clay platelets



The attraction between clay platelets can also be increased by the presence of polyvalent
cations such as calcium or aluminum. Cations cannot associate with more than one charge
deficiency on a given unit layer. If the ions carry more than one charge they may form a bridge
between clay particles increasing the level of structure in the suspension. This is illustrated in
Figure 4.15, showing calcium bridges on the edge or between the faces of two clays.
Edge-to-edge and edge-to-face associations may be formed quickly.
Face-to-face association is a more stable form of association but takes longer to form and may
require higher levels of calcium.

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Figure 4.15: Flocculation of clays by polyvalent cations


Long chain polymers may also form bridges between the clay platelets as illustrated in Figure
4.16. The polymer increases the degree of interaction between the clay platelets and hence the
viscosity. The chapter on Polymer Chemistry explains how longer chain polymers have a more
noticeable effect on viscosity.
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Figure 4.16: Action of anionic polymers




4.4.2 Repulsive Forces


The negative charges on the surface of a clay particle attract cations. These cations are usually
hydrated themselves.
The layer of water molecules next to the particle is bound to and moves with the particle. It is
termed the stern layer or bound layer.
The layer of water molecules next to the stern layer is called the diffuse layer. The density or
concentration of any cations in the diffuse layer decreases as the distance from the particle
increases. The ions in this layer may move independently of the particle.
The interface between the stern layer and the diffuse layer is called the shear plane.
Together these layers are termed the electrostatic double layer, represented in Figure 4.17.
The double layer surrounding bentonite particles may extend 200 or more from the surface.

Figure 4.17: Electrical double layer

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The effect of the electrostatic double layer causes clay platelets to repel. This effect is termed
double layer repulsion. The thickness of the diffuse layer is reduced as either the cationic
concentration or valency in the solution is increased. When this occurs, particles are able to
approach each other more closely before repulsive energies become strong enough to act. Figure
4.18 shows the effect of salt on the repulsive forces of charged particles.

Figure 4.18: Effect of salt concentration on repulsive forces of charged particles



In a suspension, the charges developed on broken clay platelet edges are influenced by the pH.
The negative charge density is increased at higher pH values because hydroxyl ions neutralize
positive edge sites. The influence of pH on charge density is demonstrated by measuring the
mobility of the clay between two charged plates. Figure 4.19 shows the electrophoretic mobility
increasing rapidly between pH 8-10. This indicates the benefit of increased pH when dispersing
bentonite and less dispersive conditions are created at lower pH values. (Above pH 12, the
dispersive affect may diminish to a point where is reversed. That is, clay particles begin to
approach each other more closely.)

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The electronegative character of a clay particle can be increased by the adsorption of negatively
charged low molecular weight molecules called polymers. They adsorb onto the positive edge
sites and increase the overall negative charge density. These molecules increase the repulsive
forces between the particles and are termed deflocculants. The decrease in inter-particulate
forces also decreases the viscosity. Therefore, they are also called thinners.

Figure 4.19: Electrophoretic mobility of Na-montmorillonite as a function of pH



Any process which changes the charge density on clay particles influences the net interactive
forces between the particles. In general, it may be stated that as the environment of a suspension
becomes more cationic in nature, clays tend to build more structure. Conversely, structure may
degrade as the environment of the suspension becomes more anionic. Table 4.4 summarizes
some of the factors which contribute to the formation or degradation of clay structures. The
overall effect of attractive and repulsive forces in a range of salt environments is shown in Figure
4.20. Note that at low electrolyte concentrations repulsive forces are able to offset the attractive
forces and the clay particles are repelled. As the electrolyte concentration is increased, the
thickness of the diffuse layer is reduced and the repulsive forces diminish to a point where the
attractive forces dominate.

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Figure 4.20: Flocculation



Table 4.4: Summary of Conditions which influence Clay Structures

ENVIRONMENT LESS STRUCTURE MORE STRUCTURE
Salt concentration < 300 mg/l > 3 000 mg/l
Fast at 20000 mg/l
pH > 8 < 6 and > 12
Cationic concentration Sodium Calcium, aluminum
Polymer type Anionic, low molecular weight High molecular weight


4.5 THE BEHAVIOUR OF CLAYS IN DRILLING FLUIDS


Wyoming bentonite is the most common viscofying clay used in drilling fluids. When a bentonite
suspension is considered, it is easy to imagine perfectly dispersed clay plates, each fully hydrated
with its own double layer. Actually this is never the case. Non-dispersed aggregates always exist
in bentonite suspensions. Soon after drilling commences, an increasing concentration of
formation clays becomes entrained in the system. It is probable that most clay-based fluid
systems eventually contain several or all of the clay minerals. As drilling continues, the pH or the
ionic environment of the suspension may change. Ultimately a complete array of particle
association types may exist in a fluid at any given time.

For this reason, the classification of clay particle associations simply refers to the net or average
effect from all types of associations existing in a fluid.
These associations are limited to four terms: Dispersion, flocculation, aggregation and
deflocculation.
The basic definition of aggregation and dispersion denotes the physical number of existing
particles, aggregation meaning less and dispersion meaning more. The terms flocculation and
deflocculation refer to the interactions between particles and the colloidal structure derived as a
result of these interactions.
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These terms are occasionally misused in our industry. The most common misuse is an outright
exchange of the term dispersion for deflocculation. Their co-use may also be quite confusing. The
terms flocculated / aggregated and flocculated / dispersed correctly refer to possible average
particle associations in clay suspensions. However, these have only limited application to most
drilling fluids and will only be touched on in this text.


4.5.1 Dispersion

As a drilling fluids term, dispersion may mean either the mechanical subdivision of particle
aggregates in a suspension or the electrochemical subdivision of clay platelet stacks. Both
processes may occur simultaneously and the net result is the same. There is an increase in the
number of clay particles. The term dispersion does not apply to the process of deflocculation.

The ability of bentonite to disperse is initially dependant on its ability to attract polar molecules
(see section 4.3.3). It must then continue to hydrate or adsorb water. The adsorption
mechanisms of water on clay surfaces are not fully understood, but the most accepted theory is
the one of hydrogen bonding. The surfaces of clay minerals are made up of either hydroxyl
groups or oxygen atoms arranged in a hexagonal pattern, which can coincide at points with a
similar pattern in a hydrogen-bonded water structure. Analysis of the hydration of smectites
shows that the swelling of montmorillonite takes place in a step-wise fashion. The reason for this
is thought to be a step-wise formation of discrete monomolecular water layers.

It is necessary for the c-spacing to increase before separation of individual unit layers can occur.
As they separate, the viscosity of the suspension increases because more separated layers
cause an increased resistance to flow. Further, a larger surface area causes more water to
become crystalline or structured close to each layer. Figure 4.21 shows diagrammatically the
possible resultant structures of clay plates when various factors influencing dispersion are
introduced. As an aid to understanding these factors, test results on actual fluids have been
included.

It can be seen with sample B and C that better dispersion occurs if hydration time or
temperature is increased. At higher temperatures increased Brownian motion accelerates
the dispersion process.
Sample D indicates that mechanical agitation increases the dispersion of bentonite. This
effect becomes very apparent when tertiary formations are drilled using high nozzle
velocities. Particle size decreases while low-gravity solids (LGS) and dilution rates increase.
The effect of pH is shown in sample E where the net negative charge at clay platelet
edges has been increased. This relates to the electrophoretic mobility increase discussed
previously.
Samples G and H show how dispersion is inhibited by the cations sodium and calcium. In
the case of the sodium solution, there is no attempt made by hydrated (larger) sodium to
exchange with sodium between the unit layers in bentonite. In the case of calcium, the
resultant properties are similar to the sodium properties, but at a much lower concentration.
This is because divalent cations can associate with two charge deficiency sites one on
each of two unit layers. Divalent calcium is more readily exchanged with the sodium in
bentonite and forms a stronger bond. Calcium is added purposely to some fluids to inhibit the
dispersion of formation clays.
Sample I shows the effect of encapsulating polymers on dispersion. The polymer, ferro-
chrome lignosulfonate has been used in this example. The results indicate that the addition
of lignosulfonates to the make-up water for pre-hydrated bentonite batches is a questionable
practice unless it is added last. They also aid in dispelling the idea that lignosulfonates cause
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formation solids to disperse. In fact, the adsorption of lignosulfonate on clay surfaces
reduces clay swelling and cleavage promoting hole stabilization and recovery of un-
dispersed cuttings.
6


Figure 4.21: Factors influencing bentonite dispersion



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4.5.2 Flocculation

Usually a flocculated system is evidenced in resultant rheological properties. Initially the fluid
becomes thicker. The funnel viscosity, yield point and gel-strengths increase. Gel strengths also
become progressive. This happens because as the clays become more structured the resistance
to flow increases. These structures or particle associations are often quite fragile and may
temporarily break during periods of shear. Thus, as suspensions become flocculated, they usually
become more shear thinning. It has been theorized that substantial increases to the yield point
indicate edge-to-edge associations and that progressive gel strengths indicate edge-to-face
associations. Increased structure also serves to degrade the fluid loss and cake characteristics of
the fluid. This is because it is difficult for associated clay platelets to lay flat against a point of
pressure differential.

The electrostatic double layer surrounding bentonite particles in a suspension becomes
compressed as the concentration of cations increases. At the point where attractive forces
become dominant, particle associations, called flocs begin to form. The critical concentration of
cations where this occurs is called the flocculation value. The flocculation value for a given
suspension may be determined by increasing the cationic concentration in the suspension.
Before flocculation the fluid appears cloudily. As flocculation begins, individual flocs become large
enough to drop out of suspension. They may even be seen by the naked eye, as in the case of
the floc-water fluid systems described in the chapter on Water-Based Fluids. These particle
associations sediment, leaving a clear supernatant fluid. The actual volume of sediment depends
upon how closely or loosely the particles are associated.

It should be noted that if the clay concentration is high enough, the division of supernatant and
sediment might only occur after centrifugation. Most drilling fluids are not subjected to such forces
for more than a few seconds during solids separation. They normally remain homogeneous. Thus
a flocculated drilling fluid is usually diagnosed through changes in its rheological properties. (See
Figure 14.24.) In most drilling fluids, there is a sufficient quantity of soluble salts to provide some
degree of flocculation or structure building. If the concentration of both clay and cation is strong
enough, individual flocs will build a continuous gel structure.

The flocculation of clay sheets may be described in three ways as illustrated in Figure 4.22. They
include; edge-to-edge, edge-to-face and face-to-face associations. In a given suspension it is
likely that all of these associations occur simultaneously. The net effect on the fluid's properties
results from an average influence of these associations. It is assumed that the initial stages of
flocculation involve mainly edge-to-edge and edge-to-face associations. Cation induced edge-to-
edge associations may be more common at higher pH, where positive sites at clay edges have
been satisfied by hydroxyls. The area of contact in face-to-face associations is vastly greater than
the others. Therefore it takes more time and higher concentrations of cations to form them.
However, they are much more stable (difficult to re-disperse). Face-to-face flocculation may be
correctly defined as aggregation (see Figure 4.23). Aggregation is discussed in section 4.4.5.

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Figure 4.22: Flocculated particle associations



Particle associations may also form when excessive heat is applied to a clay suspension. In this
case flocculation occurs when the Brownian motion induced movement of the clay particles
increases such that their normal repulsive forces are overcome. The particles become stuck
together. This phenomenon is termed thermal flocculation (see Figure 4.23).

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Figure 4.23: Dispersion, flocculation and aggregation with various salts



The pH of the suspension may also influence particle associations. In a very low pH environment,
hydrogen bonding between clay platelets may initiate aggregation. High pH environments may
result in severe flocculation. This may be caused by an OH
-
bridge occurring between positively
charged edges of clay plates, or edge-to-edge flocculation. This phenomenon is very apparent
when drilled solids concentrations (especially illite) are high and particle size is low. It may
become almost impossible to mix a sack of caustic into the active system. Figure 4.24 shows
some of the factors which can contribute to flocculation in clay systems.

A basic understanding of flocculation mechanisms can be extremely useful. Particle associations
may be seen as a benefit in terms of the contribution which increase particle size makes to
settling velocity. In fact, various polymers called selective flocculants may be used to increase the
settling rates of different types of clays. This technique applies to drilling or sump fluids being
cleaned or centrifuged and to clear water drilling fluids. The cleaning characteristics of some
fluids may be enhanced by flocculation. This is usually done to clean large debris from the hole.

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Figure 4.24: Flocculation theories


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4.5.3 Aggregation

The term aggregation as it applies to clays in drilling fluids may refer to the un-hydrated groups of
clay stacks as they occur naturally. More often the term refers to the particle associations
resulting from the reduction in size of the diffuse layer surrounding the clay platelets. This usually
occurs in a strong cationic environment. Cations approach and associate with exchange sites on
the basal surface of hydrated unit layers. The associated cations attract the basil surface of
another clay platelet such that clay platelets begin to form stacks or aggregates similar to their
original un-hydrated aggregates. This structure does not necessarily form instantaneously. It
usually starts as flocculation. As the environment becomes more cationic with either
concentration or valency, face-to-face associations increase. Thus aggregation may be thought of
as extreme flocculation and a net decrease in the number of suspended particles. This is
opposed to dispersion where there is a net increase in the number of particles. Figure 4.24-G
shows how the properties of a base fluid are affected by the introduction of aluminum. Figure 4.23
plots gel-strengths, indicating where aggregation begins. Aggregated clays exhibit poor
suspension and viscosity characteristics. This is because fewer particles and less surface area
provide less resistance to flow.

Figure 4.25: Flocculated aggregates


Unlike flocculated suspensions, the effects of aggregation are difficult to reverse. In practice, this
is seen after treating the effects of a contaminating polyvalent cation. Free cations may be
precipitated in the normal manner, and loose particle associations may be deflocculated with an
appropriate thinner. However, high gel-strengths usually remain for sometime afterward. Thus, it
is important to treat either the cause (precipitate) or the effects (deflocculate) of contaminating
cations before aggregation occurs.

Because total dispersion seldom occurs, clay aggregates usually exists in suspensions. They
also exist due to the face-to-face particle associations induced by polyvalent cations. In either
case these aggregates may form flocs themselves. The associations may be either edge-to-edge
or edge-to-face (see Figure 4.25). Thus, a flocculated / aggregated suspension can exist.

4.5.4 Deflocculation

The term deflocculation refers to the process whereby particle associations or flocs are reversed.
Structure is broken and resistance to flow is decreased. This usually begins as the environment
of the suspension becomes more anionic in nature. Specifically, flocculation may be prevented or
reversed by the addition of certain complex anions, notably polyphosphates, tannins and
lignosulfonates.
7
These compounds are referred to as thinners.

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It is believed that thinners are adsorbed at the edges of clay plates. The mechanism may be
either chemisorption or anion exchange at the crystal edge with the large multivalent anions of
the thinner. Raising the pH also neutralizes some of the positive charges on the clay edges.
Thus, maintenance of alkaline pH conditions will help to stabilize clay-based drilling fluid systems.

Figure 4.26: Effect of thinners



Figure 4.21-I demonstrated that lignosulfonate exhibited the ability to impede dispersion. The
same mechanism applies to other long-chain anionic molecules, some of which are used
primarily as thinners. Many types of thinner are acidic in nature. Sodium hydroxide is added to
clay suspensions with these thinners to help to solubilize them and to maintain the pH in the
suspension. If sodium exchanges with the native cations in the clay cuttings, increased dispersion
of the cuttings may occur as a result. Thus, in this case, deflocculation and dispersion may occur
simultaneously. It is important that drilling fluid engineers are aware of this effect so that excess
amounts of thinner are not added. The dispersive effect of the thinners may be offset by the
presence of preferentially adsorbed cations including potassium.

Table 4.5 shows that precipitation can be an effective means of deflocculation. This practice is
used in the field and is often complimented with the addition of thinners. Often fluid systems are
pre-treated with chemicals which will precipitate expected contaminants. In this way the
flocculation / deflocculation process may be avoided altogether. Conversely, if an evaporate
interval is extensive, the expected contaminant may be added to saturation levels purposely, to
avoid hole erosion. In this case, thinners must also be added simultaneously.


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Table 4.5: Deflocculation with Lignite and Na
2
CO
3

Parameter Sample 1 Sample 2 Sample 3 Sample 4
Base: 40 kg/m
3

bentonite
Base +
4 kg/m
3
CaSO
4

Sample 2 +
4 kg/m
3
Lignite
Sample 2 +
4 kg/m
3
Na
2
CO
3

600 42 58 48 51
300 33 49 43 42
Gel 0/10 3/5 21/18 6/12 8/14
pH 9.0 7.9 7.4 8.5

4.5.5 Viscosity in Water-Based Systems

The processes of hydration and dispersion increase the number of clay sheets in a suspension.
As they begin to interfere with each other, hinder each others movement, and align themselves,
viscosity is imparted to the suspension. Clay minerals impart viscosity to water-based systems
because of properties related to their colloidal size and their surface charges. Viscosity is the
result of clay-clay interactions and interactions between clay and the water phase, solids or
polymers. These interactions are created by weak chemical bonds which can usually be broken
by a shearing force.

The types of interactions between clay particles have been described as flocculation and
deflocculation respectively. A careful balance between the state of flocculation and deflocculation
imparts the optimum flow properties to the suspension.

The surfaces of clays contain hydroxyl or oxygen groups which form hydrogen bonds with water
molecules. Water also bonds with sites on the crystal edges. This results in a zone of structured
or crystalline water closely associated with the clay. Thus, the introduction of clays into water
reduces the volume of free water also building structure and resistance to flow.

Reactions between clays and polymers depend on several factors. The strength and the site of
adsorption depend on the chemical character of the polymer. Generally, negatively charged
polymers adsorb on positive edge sites. Most drilling fluid polymers are of this type. The chapter
on polymers explains how factors such as salinity, molecular weight, pH and charge density affect
clay-polymer interactions.


4.5.6 Viscosity in Oil-based Systems

Clays are also used to viscofy oil-based fluids. Organophillic clays do not occur naturally;
therefore they were not previously discussed. A brief description of their nature will proceed the
discussion of their behavior.

Smectites have the ability to adsorb certain organic molecules on their surfaces. Reacted
organophilic clays are based in this property. They are made organophillic by replacing
exchangeable cations with an organic molecule typically a quaternary ammonium salt:

Na
+
Clay
-
+ R
4
N
+
Cl
-
R
4
N
+
Clay
-
+ NaCl


The most commonly used clay is montmorillonite (bentonite).
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Hectorite is used when superior temperature stability properties are required. Hectorite, a
smectite has no aluminum, its structural charge results from the substitution of lithium for
magnesium. The most common type of cation is dimethyl dihydrogenated tallow amine (DM2HT):

N
CH
3
CH
3
DM
2
HT
DM
2
HT
Cl


The structure of the resultant clay plate is shown in Figure 4.27. The clay platelet coated with the
organic molecule is now able to disperse in a suitable organic medium.

Figure 4.27: Treatment of Na-montmorillonite with ammonium salt

Me
N Me
Me
Me
Me
N Me
Me
Me
Me
N Me
Me
Me
A Na Montmorillonite surface


Many theories have been advanced to explain how organophilic clays function; the most widely
accepted being the formation of hydrogen bonds between solvated clay platelets.

The size of the cationic molecule reacted onto the clay surface determines the spacing of the
structure. Weak Van der Waals forces between alkyl chains may account for some of the
structure of organically treated clay, but the predominant bonding forces are due to hydrogen
bonding at the exposed oxygen and hydroxyl groups on the clay platelet edges. A polar molecule
such as glycol, or alcohol can be added to induce hydrogen bonding, but in most normal oil-
based drilling fluids, sufficient water is present to activate the clays and induce a structural
development.

When low concentrations of bentonite-based organoclay are used a two dimensional structure is
formed. This is shown in Figure 4.28. The alkyl chains attached to the clay surface are fully
solvated giving rise to evenly spaced beds of clay platelets, which bond to give the supporting
structure, allowing weighting agents and cuttings to be held in suspension.

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Figure 4.28: Low concentration of fully solvated organoclay with H-bonding between platelets

O
H H
O
H
H
O
H
H
O
H H
O
H H
O
H H
O
H H
O
H H
O
H H
O
H
H
O
H
H
O
H
H
O
H H
O
H
H
O
H
H
O
H
H


Figure 4.29: High concentration of fully solvated organoclay with tighter H-bonding between
platelets

O
H H
O
H
H
O
H
H
O
H H
O
H
H
O
H
H
O
H
H
O
H
H


As the concentration of organoclay is increased the inter-platelet spacing is gradually decreased
until it reaches a distance determined by the alkyl chains. This is shown in Figure 4.29. This gives
rise to a three dimensional structure that imparts changes in rheological properties leading to
higher viscosities and gel strengths.

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Since the rheological properties imparted by organophilic clay are both pseudo-plastic and
thixotropic in nature (refer to the Rheology chapter) an increase in clay concentration does not
show as fast as a rise in plastic viscosity as it does in yield point. The reason for this is that the
greater bonding forces have more effect on rheology than simply increasing the solids
concentration would have.


4.5.7 Gelation

Gelation in water based fluids may occur at salt concentrations below the flocculation point if clay
concentrations are high enough. When diffuse layers interfere with each other, clay platelets align
themselves to a position of minimum free energy. Several theories exist, regarding the possible
particle associations which contribute to gelation. These theories encompass the entire particle
associations previously discussed.

The important considerations which lead to effective drilling fluids management are the trends in
the values obtained from measuring the strength of gel structures. For example, the presence of
contaminating ions may be detected through increased gel strengths before they are seen in
filtrate titrations. Some contaminants may never been seen in filtrate titrations. High gel strength
measurements made at elevated temperatures are usually the first indication that the mean
average particle size in the suspension is degrading.
Progressive gel strengths indicate that some type of flocculation has occurred. (Progressive
means, the strength of the gel structure is much greater after 10 minutes in a static state than
after only 10 seconds at rest). In a highly shear-thinning / thixotropic fluid, extremely progressive
gel strengths may impede the fluids ability to clean by the Bottom Hole Assembly. Sufficient
cleaning structure may not be re-established until further up the annulus.

In drilling fluids, the maximum extent of gelation should be established quickly and should not be
excessive. Prior to the cessation of circulation for long periods such as logging, a better indication
of fluids gelation characteristics can be made. This involves measuring the gel strength at bottom
hole temperatures over a more realistic period of time.


4.6 FORMATION CLAYS

4.6.1 Diagenesis

The term diagenesis refers to the process whereby sediments are converted to more competent
rock through combined physical and chemical influences, over time. The chemical influences on
sedimentary deposits may include solution / dissolution, leaching and changes in pH conditions
caused by bacterial action or the release of acidic gasses. The physical influences include
pressure and temperature.

Generally montmorillonite is associated with the youngest sediments. It is formed under basic
conditions, often in association with volcanic ash and seawater. As young sediments are
compacted, water is squeezed out of the unit layers and released as free water. Generally the
structure of clay changes from the smectite type to the non expanding types. The result depends
on the environment in which compacting occurs.
Acidic environments and fresh water conditions favor the formation of kaolinite. Kaolinite may
also be formed by leaching of feldspars and is often encountered in sandstone reservoirs.
Montmorillonite may be transformed into illite and then to mica as dehydration continues.
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If compacting occurs in a saline or marine environment, chlorite may be formed through
magnesium fixation by montmorillonite. Chlorite clays may be precipitated in sandstone reservoirs
and form the cementing mineral.
When mixed layer clays are found, it is an indication that diagenesis is in progress.

Various investigators have reproduced the diagenetic process in laboratories, using different
reagents usually under normal temperatures and pressures. Illite, chlorite and kaolinite have
been produced from smectites.
8



4.6.2 Sediments

Some borehole stability problems may be attributed to the reaction of formation clays to the
drilling fluid. Essentially, the exposure of stressed sediment to the drilling fluid may re-hydrate the
clays. When this causes increased stress, erosion or plastic deformation may occur. Sedimentary
formations are characterized by the type and concentration of mineral present and by the
pressure regime involved during consolidation. The amount of in situ water is dependant upon the
latter. Table 4.6 lists a classification of sediments. The chapter on Borehole Stability contains a
more in-depth review of sediments.

Table 4.6: Typical Classifications of Sediments
TYPE

Water content (%
w)

Clay content

MBT
(meq/100g)

Density
(g/cm
3
)

CLAY

25-70 SOFT

Montmorillonite
Illite

20-40

1.2-1.5

MUDSTONE

15-25 firm

Montmorillonite
Illite
Mix layer

10-20

1.5-2.2

SHALE

5-15 hard

Treated montmoril.
High illite

3-10

2.2-2.5

SLATE

2.5 brittle

Illite
Kaolin

1-5

2.5-2.7

LIMESTONE


100-80% calcium
carbonate

0 2.5-2.8

MARL
70-40% calcium
carbonate +
30-60% clays
0-2

1.8-2.2
CALCAREOUS
MUDSTONE
15-60 firm

10-40% calcium
carbonate +
90-60% clays
0-5 1.3-1.8

Clays are found in production sands in small but significant quantities. The clays deposited with
the sand are termed detrital. With the passage of time, clays and associated minerals undergo
diagenesis and new clay crystals may be formed. They form on the surface of the sand,
occupying an important position as a potentially water wet material lining the pore throats. The
clay minerals described in this chapter all commonly occur in sandstone reservoirs. They respond
to the same changes in the chemical environment that have been described for drilling fluids.

Drill in, Completion and Production fluids may be designed to minimize the tendencies of certain
clays to cause pore throat blockage by swelling or migrating. This subject is discussed in greater
detail in the chapter on Production Zone Drilling, Completion and Workover Fluids.
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4.6.3 Clay Analysis

Various types of clay analysis are performed by companies involved with drilling fluids. Tests are
conducted on commercial clays to ensure they will perform in field applications. Often, tests are
conducted on formation clays to discern the best methods of insuring formation stability while
drilling.

Understanding the mechanisms behind clay swelling and dispersion has led to the development
of several types of inhibitive, water-based drilling fluid systems. These systems use one, or a
combination of three possible means of reducing clay swelling. These include:
Increasing the attractive forces or cationic environment to reduce electro-static repulsion
(bentonite won't hydrate in calcium solutions);
Controlled cation exchange as in potassium salt fluids;
The use of various types of encapsulating polymers.

Formation clays may be collected for sampling during the course of drilling a well. The most
representative samples are obtained from clay which is scraped from the Bottom Hole Assembly
on a bit trip. If this sample is dry inside, interference to the test results caused by drilling fluid
induced cation exchange may be minimized. Also, commercial bentonite concentrations won't
have to be factored out of the results.

Several methods are available which evaluate the type and concentration of clay minerals
present in a hydrating and / or swelling formation. The first step in solving clay related problems is
usually to perform an X-ray diffraction analysis. This technique indicates the presence and
concentration of all minerals in the bulk sample, including quartz, dolomite, etc. The clay fraction
itself is also categorized, indicating the percentages of all clay minerals including mixed layer
clays.

Knowing the types and percentages of clays present, leads to further tests, involving specific
inhibiting fluids. These include:
Shale inhibition tests;
Capillary-suction timer tests;
Dispersion tests.

These results lead to the application of the most efficient inhibition mechanisms for a given
formation. The optimum concentrations of inhibiting chemicals may also be determined from
these tests.

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References

1 H.C.H. Darly & George R. Gray, Composition and Properties of Drilling and Completion
Fluids, 5th ed. (Houston: Gulf Publishing Company, 1988), 146.

2 Darley and Gray, Composition and Properties, 146.

3 Preston L. Moore, Drilling Practices Manual (Tulsa: The Petroleum Publishing
Company, 1974), 80.

4 Darley & Gray, Composition and Properties, 150.

5 van Olphen, H. , An Introduction to Clay Colloid Chemistry, 2nd ed. (New York: John
Wiley & Sons, 1977), 12.

6 Browning, W. C. & Perricone, A. C. Lignosulfonate Drilling mud conditioning agents,
SPE Paper 432, Annual meeting, Oct. 7 - 10, 1962.

7 Darley & Grey, Composition and Properties, 167.

8 Ralph E. Grim, Clay Mineralogy, 2nd ed. (New York: McGraw-Hill Book Company,
1968), 488.
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CHAPTER 5

POLYMER CHEMISTRY


5.1 KEY POINTS AND SUMMARY

5.2 INTRODUCTION TO POLYMER CHEMISTRY AND TERMINOLOGY
5.2.1 Building Units
5.2.2 Some Characteristics of Drilling fluid Polymers
5.2.3 Charges on Polymer Molecules
5.2.4 Categorizing Drilling fluid Polymers
5.2.5 Polymer Modification

5.3 POLYMER STABILITY
5.3.1 Wellbore Temperatures
5.3.2 Chemical Stability
5.3.3 Electrolytic Effects
5.3.4 Biological Stability
5.3.5 Shear Stability
5.3.6 Lab Measurements
5.3.7 Operational Aspects

5.4 FUNCTIONS OF POLYMERS IN DRILLING FLUIDS
5.4.1 Viscosity
5.4.2 Fluid Loss Control
5.4.3 Shale Stabilization
5.4.4 Flocculation and Extension
5.4.5 Deflocculants
5.4.6 Surfactants

5.5 POLYMER DESCRIPTIONS
5.5.1 Starch and Modified Starch
5.5.2 CMC and PAC
5.5.3 HEC
5.5.4 GUAR Gum
5.5.5 Xanthan Gum
5.5.6 Scleroglucan
5.5.7 Lignosulfonate
5.5.8 Polyacrylamide
5.5.9 Polyacrylates
5.5.10 Polyalkylene glycols
5.5.11 Descriptions of other Polymers

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5.1 KEY POINTS & SUMMARY

Since starch was first used in Drilling fluids over 50 years ago, the development and application
of various polymers has become an accepted norm in Drilling fluids engineering. Polymers
enhance many functions of Drilling fluids from lubrication to viscosity, in fact, polymers are able to
enhance or perform almost all of the functions of Drilling fluids as outlined in chapter 1.

Factors affecting the performance of polymers include: shear conditions, time, temperature,
salinity, alkalinity and the presence of microorganisms. When polymers are used during drill-in or
completion operations, the possibility of formation pore plugging and the polymers solubility in
acid must be considered. The diversity in both the composition and properties of drilling fluid
polymers makes a critical examination of the factors involved in polymer selection imperative.
This chapter begins with a brief look at polymer chemistry. Functions of polymers and their
relationship to the environment of the solution are discussed next. Finally, descriptions of some of
the most common drilling fluid polymers are given.

This chapter should be considered as an introduction to drilling fluid polymers.


5.2 INTRODUCTION TO POLYMER CHEMISTRY AND TERMINOLOGY

5.2.1 Building units

The term polymer refers to large or macromolecules which are built up from small, simple
chemical units called repeating units or monomers. A single polymer may contain thousands of
monomers. Figure 5.1 depicts a single cellulose monomer.

Figure 5.1: Cellulose monomer

OH
OH
O
O
O
OH
O
OH
O
OH
HO
Monomeric unit


In the 19th century the term colloid was proposed to distinguish polymers from materials which
exist in crystalline form. Today a colloid is often defined as a substance which consists of
particles too small for resolution with an ordinary light microscope, diffracts a beam of light, and in
suspension fails to settle out. Most drilling fluid polymers are termed organic colloids.

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Polymers may be found in nature and in fact, some have been used for thousands of years.
These include natural resins, gums, asphalt and amber. The term polymerization refers to the
natural formation of, or the synthesis of polymers. It may be considered as the process whereby
monomers are joined together to form polymers. The longer the reaction takes place the longer
the polymer.

Figure 5.2:

OH O
Acrylic acid
Ph
3
C
OH O
H
OH O
OH O
H
Ph
3
C
OH O
H
Ph
3
C
+
OH O
+
ETC!!!
O OH OH O OH O
n
n-polyacrylic acid


The sale of monomeric compounds is a base industry. Polymer manufacturers purchase various
types of monomers and synthesize polymers by proprietary methods (fig 5.2). Variables to the
polymerization environment include pH, temperature, time and the medium in which the process
occurs. Polymerization can occur in the water phase of an oil emulsion or in liquid CO
2
.


5.2.2 Some characteristics of Drilling fluids polymers

Many types of polymers are used in the Drilling fluids industry today. (Polymer functions are
discussed in Section 5.3). The ways in which polymers behave and alter the properties of a
solution depend on several variables in the polymer's molecular structure. These are incorporated
into the composition of individual polymers. Often, only small variances in a polymer's structure
can drastically change its affect in a solution.

Variables, which affect polymer characteristics, include:

1. The number of monomers linked to form a polymer chain.
2. The number of different types of monomers present in a polymer molecule and the order in
which they occur.
3. The shape and structure of the molecule.
4. Electrolytic variables including the net charge, and the position and density of the charge.
5. The chemical and structural modification of a polymer, subsequent to polymerization.
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Figure 5.3 indicates how polymers may be classified according to the variables mentioned above.

Figure 5.3: Classification of polymers

Low MW

A
Linear
Hi MW

B
HomoPolymers
Non-
Linear
Branched

C
Alternate

D
Block

E Linear
Random

F
Co-Polymers
Non-
Linear
Crosslinked

G


The number of monomers in the chain specifies the length of the polymer chain. This number is
usually referred to as the degree of polymerization or DP.
The molecular weight of a molecule refers to its mass. It is the sum of the atomic weights of its
constituent atoms. The molecular weight of a polymer molecule is not "the chain length" as is
sometimes claimed. Rather, it is the product of the mass of its monomers and its degree of
polymerization.

In a given polymer, the terms molecular weight, degree of polymerization, and chain length are
usually interdependent. That is, when the numerical value of one increases, the value of the
others also increases. This is the reason why the terms are sometimes used interchangeably.

When polymers are being synthesized, the ultimate degree of polymerization may be controlled
by either the solubility of the polymer chains or by controlling the number of "terminating
monomers" (fig 5.4). In free radical polymerization this may be accomplished when two free
radicals react to annihilate each other.
1


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Figure 5.4:

Ph
3
C + Ph
3
C
Ph
3
CCPh
3
Chain termination


The molecular weight of an individual polymer is extremely important. Identical polymer structures
may act either as a clay flocculant or deflocculant in a drilling fluid, depending on the polymer's
molecular weight. Molecular weights of drilling fluid polymers typically vary from thousands to
millions. Figure 5.3A and 5.3B indicate two polymers with similar constituent monomers but
dissimilar molecular weights.

For an application such as selective flocculation where a polymer's effectiveness is critically
dependant on its molecular weight, its molecular weight distribution curve becomes another
important factor. In the case of the wide distribution curve, it is possible and probable that
molecules on the extreme right or left side of the curve will interfere with, and reduce the
effectiveness of the polymer. This is where quality control plays an important function in
manufacturing drilling fluid polymers.

When two types of monomers are present, the molecule may be defined as a co-polymer.
Figures 5.3D 5.3G show some of the possible structures of co-polymers. Unfortunately, the 3-
dimensional aspects of these cannot be depicted on paper. Polymers with 3 different types of
monomers are termed terpolymers.

Polymer shape may be categorized broadly into 3 groups: linear, branched and cross-linked.
A cross-link defines a covalent bond joining two polymer molecules at a point along at least one
of the chains, (as opposed to at the end of the chain). Cross-linking may be induced by the
introduction of a cross-linking agent as depicted in Figure 5.3G. Polymers in drilling fluid solutions
are often cross-linked by a free cation.

Cross-linking may radically alter the properties of both the polymer and the resultant solution.
This is caused either by the increase in molecular weight and / or a reduction in the solubility of
the molecule after cross-linking. The shape of a solvated polymer molecule is important because
it affects the way the polymer reacts to other (especially insoluble) components of the solution.
The ultimate shape of a polymer molecule is dependant on several factors.


5.2.3 Charges on Polymer Molecules

Drilling fluid polymers may carry electrostatic charges. When they do, they are termed
polyelectrolytes. An electrolyte is a substance that, when dissolved in a suitable solvent,
becomes an ionic conductor. The behavior of solvated polymers is dependant on their ionic
character. Drilling fluid polymers may be categorized as:

1. Nonionic
2. Anionic
3. Cationic

Drilling fluid polymers are usually anionic or nonionic since cationic polymers tend to flocculate
clays. Chemical reactivity can be built into a polymer either by the polymerization of monomers of
different chemical character or by chemically modifying an existing polymer.

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Table 5.1 lists the common nonionic chemical groups typical of drilling fluid polymers. An
important function of these is that they all readily form hydrogen bonds with water. This
contributes to the polymer molecule's ability to hydrate and ultimately to solvate. Because
nonionic polymers have no dissociable inorganic radical, they have greater stability in highly
saline environments.
2
Starch, Guar Gum, and Hydroxyethyl Cellulose (HEC) are all nonionic
polymers.

Table 5.1: Non-Ionic Chemical Groups that Contribute to Reactivity of Polymers

Chemical Formula Name
R OH

Alcohol
O
R Me

Ether
R NH
2
O

Amide
N O
R

Pyrrolidone
R N C O

Isocyanates
R X Alkyl halides
R

Alkenes


The Clay Chemistry Chapter (4) explained that, as the concentration of available anions
increased in a fluid suspension, the strength of the associations of clay particles became less
prevalent. Generally, low molecular weight, anionic polymers impart less viscosity to a fluid and
are therefore desirable in systems containing solids. By controlling certain parameters such as
the degree of polymerization, anionic polymers can be made to contribute to a desired degree of
viscosity. Figure 5.20 shows anionic polymer acting as a deflocculant, while Figure 5.19 shows
the same polymer, but with a higher molecular weight performing as a bridging agent or
flocculant.

CMC (carboxymethyl cellulose), PAC (polyanionic cellulose) and PHPA (partially hydrolyzed
polyacrylamide) are common examples of anionic polymers. Typical anionic groups are given in
Table 5.2. The most common group is the carboxylate group found in CMC and Polyacrylates.
The sulfonate group is common in calcium tolerant polymers.

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Table 5.2: Anionic Chemical Groups that Contribute to Reactivity of Polymers

Chemical Formula Name
RO P
O
O
-
O
-
2M
+

Phosphate
R P
O
O
-
O
-
2M
+

Phosphonate
R O
-
M
+
O

Carboxylate
R S
O
O
O
-
M
+

Sulfonate
RO S
O
O
O
-
M
+

Sulfates
R N
O
H
S
O
O
-
M
+
O

Amido-sulfonates


When inorganic anions became dissociated from a polymer chain, the polymer becomes cationic
or positively charged. Cationic polymers are not commonly used in Drilling fluids because of
their flocculation effect on clays. They serve mainly as emulsifiers and wetting or surface-active
agents. Table 5.3 lists some cationic chemical groups, which contribute to drilling fluid polymer
reactivity.

Table 5.3: Cationic Chemical Groups that Contribute To Reactivity of the Polymer

Chemical Formula Name
R NH
3
+
Cl
-

Ammonium Salts
R N
+
(CH
3
)
3
Cl
-

Quaternary Ammonium Salts


The charges or functional groups on polymer chains can cause variances in the shape of the
molecule in solution, depending on the environment of the solution. If the functional groups on a
polymer molecule are similar, their natural repulsion in solution causes the molecule to stretch
out. This tendency may be either limited or enhanced, depending on the nature of the
environment. The effectiveness of a polymer molecule in solution is extremely dependant on its
shape. This is especially applicable to branch-type viscofying and filtration control polymers.
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5.2.4 Categorizing Drilling fluid Polymers

Drilling fluid polymers are often classified after their origin, as follows:

1. Natural polymers
2. Modified natural polymers (sometimes called semi-synthetic)
3. Synthetic polymers.

Natural polymers originate in nature as plant constituents or exudates. The monomers of natural
drilling fluid polymers are carbohydrate-type (sugar like) molecules (fig 5.5). The monomer for
either cellulose or starch is glucose.

Figure 5.5:
O
OH OH
OH
OH
HO
Glucose


How can the same monomer give two different polymers? Polymers that are very different from
each other, for one you can eat starch but not cellulose (fig 5.6).
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Figure 5.6:



Every second glucose is turned backwards and linked to the polymer. Most natural polymers are
variations on this theme.

When a natural polymer is altered by chemical means, it is called a modified or semi-synthetic
polymer. Natural polymers are modified to enhance certain characteristics of the polymer. These
might include: water solubility, salt tolerance, tolerance to multivalent cations and resistance to
bacterial degradation. CMC, modified starch, HEC, CMHEC are all examples of modified
polymers (figure 5.7).
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Figure 5.7:



Synthetic polymers are usually manufactured by using chain-reaction polymerization, starting
with fairly simple monomers. These bonds are difficult to break, making synthetic polymers less
susceptible to various types of degradation than natural polymers. The reason for this is the non-
natural manufacture of synthetic polymers, which inhibits enzymatic degradation.

In most instances this is beneficial unless degradation characteristics are required, as in the case
of well stimulation with acid. The selection of monomeric types becomes more diverse as the
specific applications for synthetic polymers increase.


5.2.5 Polymer Modification

The length, shape, charge and type of functional group may be altered on a polymer molecule
subsequent to polymerization. This is done to enhance the effectiveness of the molecule with
respect to a drilling fluid property or function. These might include solubility, resistance to harsh
environments and specialized functions such as encapsulation. Although the process is usually
complicated, ultimately the cost-effectiveness of the product is improved.

One such process, defined by the term degree of substitution (DS) is performed on the
cellulose group of polymers. The cellulose monomer depicted (previously) in Figure 5.1 is by
itself, insoluble in water. It is made soluble by reacting one or more of its functional groups (an
OH group) with chloroacetic acid in the presence of a base. CH
2
COO
-
Na
+
is substituted for H
+
.

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Figure 5.8:
OH
OH
O
O
O
O
O
OH
O
OH
O
O
Na
+-
O
O
-
Na
+
O
Substituted Monomeric unit


The expression CH
2
COO
-
is a form of CH
2
COOH, which is referred to as a carboxyl group, a
monovalent anion, typical of organic acids. After the reaction, the molecule is referred to as
carboxymethyl cellulose (CMC).

The carboxyl group imparts solubility to the cellulose monomer (fig 5.8). Further, in solution the
sodium ion disassociates easily, leaving negative sites along the chain. The mutual repulsion of
these sites helps the chain to stretch out, increasing the viscosity of the solution. Originally there
were three OH groups on the cellulose unit, each capable of substitution. In the case of CMC, the
term degree of substitution refers to the average number of carboxyl groups on the chain per unit
cell or monomer.

Hydrolysis is a term used to describe the reaction of water (hydro) on a type of functional group
to give two or more new compounds (fig 5.9).

Figure 5.9:
R NH
2
O
H
2
O
R OH
O
+ NH
3
amide carboxylic acid


It typically means the replacement of a functional group in this case NH
2
with OH. As a Drilling
fluid term it usually refers to a process whereby the polyacrylamide (copolymer) molecule is
restructured to perform certain functions more effectively. A 30% hydrolyzed polyacrylamide
performs very efficiently as a shale encapsulator (fig 5.10).

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Figure 5.10: Polyacrylamide

O NH
2
NH
2
O NH
2
O
n


Figure 5.11: Partially Hydrolyzed (with OH) Polyacrylamide (PHPA)

O NH
2
OH O NH
2
O
n


Different degrees of hydrolysis promote increased efficiency of the polymer with respect to other
functions. These can include filtration control and clay flocculation. Partially hydrolyzed
polyacrylamide is referred to as PHPA.

Sulfonation is another process, which alters the structure of a polymer molecule. Phosphate and
especially sulfate reduce a polymer's tendency to form complexes with multivalent cations such
as calcium. Calcium tolerance can be increased when certain functional groups such as
carboxylate are replaced with sulfate (see Table 5.2). The prefix "sulfonated" is added to the
polymer name to indicate this process has occurred. Sulfonated styrene maleic anhydride is a
good example. A classification of types and functions of drilling fluid polymers is given in Table
5.4.
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TABLE 5.4: Classifications of drilling fluid polymers

NAME FUNCTION
MOLECULAR
WEIGHT
CHARGE / SHAPE
Natural Polymers
Starch
(Corn, Potato Starch,
)
Fluid loss control in saline
Environments
40 10
5 Anionic/Branched
Linear
Guar Gum
Viscosity in fresh or saline
solutions. Fluid Loss Control
210
5

Nonionic/Branched
(May have some
anionic groups)
Modified Polymers
Hydroxyethyl cellulose
(HEC)
Viscosity especially in
completion fluids
Nonionic/Linear
Carboxymethyl
cellulose
(CMC HV CMC HV)
Viscosity and fluid loss control
at high MW (HV)

Fluid loss control at low MW
(LV)
Diverse
Anionic/Linear


Anionic/Linear
Polyanionic Cellulose
(PAC RG PAC SL)

Viscosity control at high MW
(RG)

Fluid loss control at low MW
(SL)
Diverse
Anionic/Linear

Anionic/Linear
Xanthan Gum
(XC XCD)
Viscofier in fresh or salt water
thixotropic properties
510
6
2010
6
Anionic/Branched
Lignosulfonate
Deflocculant and Fluid loss
control
10
3
2010
3
Anionic/Branched
Lignite
Deflocculant and Fluid loss
control
10
3
2010
3
Anionic/Branched
Synthetic Polymers
Polyphosphates (SAPP) Deflocculant Anionic
Acrylic Polymers
Polyacrylmide (PHPA)
Encapsulator and Clay
Flocculant
> 310
6

Average
10
6

Anionic/Linear
Sodium Polyacrylate
(PA)
Temperature stable
Deflocculant
Fluid Loss Reducer
710
3
1010
6
Anionic/Linear
Sulfonated
Styrene/Maleic
Anhydrite (SSMA)
Hi Temp Deflocculant 1000 5000 Copolymer
Sulfonated Vinyl
Copolymer (VAVS)
Hi Temp Fluid Loss Control
Secondary Viscofier
110
6
210
6
Copolymer



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5.3 POLYMER STABILITY

Polymers contain chemical bonds and functional groups, which may undergo reactions initiated
by wellbore conditions. These include temperature, pressure, oxygen, pH, trace metals, free
radicals and shear rates. This section examines the influence these conditions may have on the
stability of polymers. The significance of laboratory tests compared to field experience is also
discussed.

The term polymer degradation refers to a type of cleavage in the polymer molecule or chain,
usually at the weakest bond. The term de-polymerization is sometimes used to express this
effect. Degradation does not refer to a reduction in product effectiveness caused by a structural
collapse of the molecule.

There are a number of processes, which contribute to polymer degradation. These may destroy
the monomer, monomer bonds, the acetyl linkage or cause a chemical alteration in side chains or
functional groups.


5.3.1 Wellbore Temperatures

The temperature of the earths crust tends to increase with depth at a rate defined as the
geothermal gradient, expressed in C/Km (or F/100 ft). The heat flow in the upper crust is
derived from conducted heat from the lower crust and mantle, and radiogenic heat in the upper
crust. These factors generate a range of geothermal gradients from 8 50 C/Km depending on
the location. Temperature influences the rate of chemical reactions, approximately doubling for
every 10C rise in temperature. Temperature gradients are discussed thoroughly in the chapter
on High Temperature Drilling.

Thermal degradation or decomposition is a factor which limits the use of most drilling fluid
polymers. As the wellbore temperature increases, this degradation may be compensated for by
the addition of fresh polymers. However, the rate of decomposition increases with temperature
until eventually it becomes extreme. This can lead to undesirable conditions, especially if the
degrading polymer is a viscofier, and Barite begins to settle.

One should also be aware of the difference in the dynamic and static rates of degradation. Under
static conditions, the fluid in the hole is subjected to much higher temperatures for longer time
periods without having the benefit of supplementation with fresh polymers.

Generally, organic polymers begin to degrade at a static temperature of 80 C. There are
differences in thermal stability within this group due to the influences of branching and
substitution. The temperature limitations depend very much on the individual manufacturing
process so it is wrong to class the temperature stability simply by polymer type. Sharp increases
in the rates of degradation occur at 110 C for most starch-based polymers and at 140 C for
most cellulose derivatives.
Lignosulfonates are usually more stable, they begin to degrade at around 120 C. Drilling fluid
properties must be controlled with synthetic polymers in high temperature wells.

The maintenance of fluid properties at elevated temperatures is most easily achieved when the
system is deflocculated. If the expected static wellbore temperature exceeds the stability of
organic deflocculants, then synthetic products must be used.

Many hot wells are also over-pressured and most high temperature / high pressure drilling fluid
systems are specifically tailored to individual wells. This usually requires extensive testing of
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products and systems to insure optimum product compatibility and system performance. The
more highly substituted CMCs, cross linked starch and Xanthan Gum all exhibit better tolerance
to higher temperatures.


5.3.2 Chemical Stability

Variations in the chemical environment can have a profound affect on the chemistry and structure
of polymer molecules. Actual de-polymerization may occur. Degradation or change in the
chemistry of the side chains may also occur. The pH, oxygen content, and the availability of metal
ions are the most significant contributors to chemical degradation.

Natural polymers are the most susceptible to chemical degradation because they usually have a
glycosidic bond or an acetyl bond (see Figure 5.12). The glycosidic bond undergoes hydrolysis
under alkaline and acid conditions with the minimum rates at pH values of 8.5 9.5. The bond
can also undergo oxidative scission, which may be catalyzed by metal ions such as iron and
nickel. The degradation may take place through a free radical reaction.

The intentional degradation or de-polymerization of those natural polymers containing an acetyl
bond is accomplished by the exposing them to hydrochloric acid. (An acetyl bond is a carbon
atom bonded singly to two oxygen atoms and at least one hydrogen atom as depicted in Figure
5.12)

Figure 5.12: Starch unit

O
O
OH
OH
OH
HO
O
OH OH
OH
HO
Acetyl link


Higher degrees of substitution in Cellulose polymers reduce the rate of chemical degradation
probably by introducing a steric factor into the reaction, blocking the susceptible sites. Thus, the
more highly substituted types of CMC, referred to as PAC are more resistant to chemical
degradation. Xanthan Gum is more stable, possibly because of the side chains and helical
structure. Unprocessed starch is very susceptible to chemical degradation but cross linking and
substitution can raise the stability to that of Xanthan Gum. The relatively low degree of
substitution of HEC makes this polymer one of the more susceptible to chemical degradation,
especially in acidic environments.

The carbon-carbon bond of the synthetic polymers is considerably more stable than the
glycosidic bond of the natural polymers. However, at higher temperatures, the side chains of any
polymer may undergo reactions such as hydrolysis (fig 5.13). An example is the hydrolysis of an
amide group under alkaline conditions, to an acid salt with the evolution of ammonia.

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Figure 5.13: Hydrolysis of amide group

R NH
2
O
NaOH
R ONa
O
+ NH
3
amide Sodium carboxylate


Yang and Treiber
3
did work on the chemical stability of polyacrylamides in water flood
applications in 1985. Their results indicated that, although degradation was increased by metal
ions, pH, and redox reactions, mainly the oxygen content of the fluid governs the rate and extent
of degradation. Thermo-oxidative degradation of synthetic polymers may occur by the
combination of oxygen with metals to create hydro-peroxides, these molecules break down easily
affording oxygen radicals that can cleave bonds in polymers.

When attempting to enhance the chemical stability of drilling fluid polymers, the pH of the fluid
should be adjusted in the range 8.5-9.5 with moderate levels of caustic. Some systems use
magnesium or potassium hydroxide as a buffer. Another approach is to minimize the oxidative
and free radical reactions by adding in radical scavengers, such as phenolic (C
6
H
5
O
-
) groups
and oxidizable groups such as an aldehyde that are preferentially oxidized. Nitrogen compounds
also neutralize free radicals and buffer the system. Inorganic compounds such as sulfur and
sodium sulfite are also very good oxygen scavengers. Lignosulfonates and tannin extracts also
provide the phenolic groupings.


5.3.3 Electrolytic Effects

The relationships between the ionic character of a polymer molecule and the electrolytic
environment were discussed briefly in Section 5.2.3. In solutions, polymers with similar ionic
charges on their functional groups tend to elongate. This is due to the mutual repulsion of these
charges. (See Figure 5.14a). The pH of the solution can affect the nature of the functional groups
and thus, the ionic character of the molecule. When this effect changes the degree of repulsion or
attraction within the molecule, its shape in the solution can change.

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Figure 5.14: Salting out effect (increase of salt concentration) on aqueous solutions of polymers



The addition of a salt to a solution (salting out) usually reduces the electrostatic repulsion of the
functional groups along the polymer molecule. If this occurs, the polymer's structure collapses as
shown in Figure 5.14b and c. Because the effective surface area of the polymer is reduced, there
is less interaction between the polymer and the other components of the fluid. The most
noticeable effect is usually a reduction in viscosity. The introduction of nonionic functional groups
to a given molecule may enhance its effectiveness in saline environments. An example of this is
the addition of ethylene oxide to CMC to form CMHEC.

Polymer molecules in solutions may also be affected by the presence of multivalent ions. Free
calcium ions can collapse the structure of a polymer molecule, netting a similar affect that salts
cause. Calcium and other multivalent cations can also effectively crosslink or bridge polymers,
resulting in decreased viscosity, solubility, and eventual precipitation (see Figure 5.15). The
adverse effect of calcium on Xanthan Gum is increased at higher pH values. This is probably due
to the precipitation of polymer-metal hydroxide complexes. All of the viscosity characteristics of
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an Xanthan Polymer system can be destroyed permanently if cement contamination is severe.
The effect of drilling anhydrite on PHPA is to cause a sharp reduction of sediment in the standard
floc test.

If Polyacrylate or Polyacrylamide contain high degrees if carboxylate groups, the partial
hydrolysis of functional groups can be accelerated by the presence of multivalent cations.

Figure 5.15: Effect of multivalent ions (Ca
+2
)

Ca
++
O
-
O
O
O
-
O
-
O
O
O
-
O
-
O
O
O
-
O
-
O
O
O
-
Ca
O
O
O
O
Ca
O
O
O
O
Calcium bridges


5.3.4 Biological Stability

All living organisms produce a variety of proteins needed to carry out functions that let them
survive and grow. Enzymes are a specialized form of a protein that allows reactions to occur
easier then normal, pretty much like a catalyst. An enzyme is a complex protein made from 20
different types of amino acids. One of the main sources of energy for all living organisms is
carbohydrates, like starch, which is made up of glucose molecules. Enzymes are used to break
down carbohydrate polymers so that the glucose units can be used for energy.

Bacteria are microscopic organisms present in almost any type of media or surface. They are
present on your hands, your car and in water. Natural polymers in water based mud systems can
be susceptible to bacterial degradation. When you provide an energy source for the bacteria
they can grow very rapidly and if left unchecked, could completely eat the entire natural polymer
in your mud.

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Natural polymers are susceptible to biological degradation because of the enzymes bacteria use
to degrade the polymer. Starch is most susceptible as it is a "storage" carbohydrate. Chemical
treatment and cross-linking of the chains in starch increases its resistance to biological
degradation. When starch is used in salt saturated systems, degradation is reduced substantially.
Other polymers, which support biological growth, include Xanthan Gum and Guar Gum. The
substitution of some of the functional groups on cellulose polymers makes them much more
resistant. Elevated temperatures and salinity may increase bacterial growth, while high pH
conditions inhibit it. However, the enzymes themselves, if they are present, are not possible to
eliminate.

It is important to recognize in advance, when a fluid environment might promote the bacterial
degradation of a polymer proposed for use. Bacterial degradation, with a complete loss of fluid
loss properties throughout the entire system can and has occurred in a matter of a few hours. If
Sulfate-Reducing Bacteria (SRB) are present, a by-product, H
2
S may be released at surface in
lethal concentrations. Synthetic polymers are not usually susceptible to bacterial degradation
because enzymes are not used to make the polymers.

In some cases killing the bacteria with a bactericide does not remove your problem. The enzymes
contained within the bacteria are still breaking down the polymers in the mud. Denaturing the
enzymes will eliminate the problem from the mud system.


5.3.5 Shear Stability

If the concentration of a given polymer is high enough, the interaction between adjacent
molecules may increase their effective molecular weight. The breakdown of these "aggregates"
may lead to a partial loss of some properties, especially viscosity.

A decrease in the degree of these molecular associations is sometimes referred to as the aging
effect. This is known to occur in static solutions. It is thought to be caused when aggregates
disentangle due to segmental motion of chains or Brownian movement of the fluid.

Increased agitation or shear can accelerate this effect. Although the results are not as noticeable
as other types of degradation and can be remedied with fresh additions of polymer, Drilling fluid
Engineers should be aware that they exist.

Some applications for PHPA polymers require that they be added through a chemical barrel.
Studies have shown that when electric agitators are used, the shear rates generated can be
excessive enough to irreversibly break polymer chains. This can effectively reduce the polymer's
ability to function as an encapsulator.


5.3.6 Lab Measurements

Lab testing does not always provide an accurate prediction of polymer performance under field
conditions. The temperature regime generated by a hot rolling oven may give longer exposure
time to higher temperatures if the oven is set at the bottom hole temperature. This is due to the
rapid temperature equilibration of the metal containers.

The entrained oxygen levels in lab fluids can be higher than those of a real fluid system since the
mixing procedure promotes oxygen saturation. Tests have shown that scavenging the oxygen by
such processes as nitrogen purging and application of a vacuum increases polymer temperature
stability in the laboratory. The stainless steel used in high temperature aged cells can catalyze
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oxidative degradation. These ions might not be present at such high concentrations in a real fluid
system.

The most important factor is that the laboratory tests generally use pressures in the range 500
2000 psi rather than the very high pressures that are present in the actual circulating system. This
is important because a de-polymerization reaction tends to increase the volume occupied by the
molecule. Since elevated pressures reduce the rate of a reaction and volume increase, de-
polymerization can be substantially lower in a real situation. This phenomenon was well illustrated
where PAC was successfully used in a well with a BHT of over 200 C. Samples from the well
were tested with the conventional equipment and the fluid deteriorated significantly. When it was
aged at the appropriate pressure as well as temperature, it tested as found in field practice.

Care must be taken when laboratory results are used to select systems for field use. Ideally the
test should be conducted at the same temperature regime and pressure conditions, as those
expected in the field.

The laboratory measurements, which are normally carried out, measure changes in properties
when tested under normal laboratory conditions. For example, viscous properties are usually
measured at atmospheric pressure and at a maximum temperature of 95 C. Fluid loss is
measured under static conditions with a maximum temperature of 200 C and differential
pressure of 500 psi. The viscous properties particularly may be different if measured at realistic
down-hole temperature and pressure conditions. When using polymers, the maximum amount of
data should be collected and field conditions monitored carefully to ensure that the drilling fluid is
operating as designed.


5.3.7 Operational Aspects

Most polymers are supplied in powder form and must be mixed on site. In order for them to
function properly, a two-step process must occur.

1. The first step involves dispersing the dry polymer in the solution. Dispersion means the
subdivision of particles. When the powdered particles are properly dispersed, water
molecules can quickly penetrate the solid polymer network and hydrogen bond to available
sites on the polymer chain. This causes the polymer to swell, exposing new bonding sites.
Eventually a layer of partially immobilized water molecules surrounds the molecule. The
result is a swollen gel. The time for this process to occur efficiently may be reduced if either
the shear rate or the temperature of the solution is increased. When a polymer molecule is
fully hydrated, its effective size or hydrodynamic volume is larger than its molecular size.

If the dry product is mixed to quickly, wetting of the exterior affects a barrier. This prevents
further penetration of water and subsequent dispersion of polymer particles. The resultant
polymer balls are called fish-eyes. Their presence indicates a need for slower mixing,
increased shear or a surface wetting agent.

A surface wetting agent can be used to overcome the high surface tensions and wetting
energies involved when adding polymers to water and salt solutions. When either liquid or
powdered PHPA polymers are mixed through a barrel, salt, such as KCl, may be added to the
water first. The cation, K
+
impedes hydrogen bonding and subsequent swelling. Again the
fluid remains thin. (Divalent ions should not be used for this purpose). A further addition of
DSTR-1-WBM to the salt system accelerates the hydration of the dispersed polymers.

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2. The second step is the solution process. Here the gel gradually disintegrates into a true
solution. (A true solution is a single-phase, liquid system). For some very high molecular
weight polymers, this may take days or weeks. Consider natural rubber dissolving into diesel
oil. Agitation may speed up the solution process.

It has been theorized that branched polymers are more readily soluble than their linear
counterparts of the same chemical type and molecular weight. On the other hand, cross
linked polymers probably do not dissolve, but only swell, if in fact they interact with the
solution at all.
4


When maintaining a drilling fluid system which employs polymers (sometimes four or five different
types are used together) it is important to know the limitations of each product. This pertains to
well bore conditions and the fluid's electrolytic and biological environment. The difference
between static and dynamic degradation and performance should also be considered. Further,
the limitations of the available surface equipment dictates the time required for mixing and should
also be taken into consideration. When contaminants such as cement, anhydrite or bacteria are
expected, the application of proper pre-treatments becomes mandatory. Two polymers may either
compliment or hinder each others performance. The necessity for pilot testing on site and in the
laboratory cannot be stressed enough, especially when changing products or concentrations.


5.4 FUNCTIONS OF POLYMERS IN DRILLING FLUIDS.

5.4.1 Viscosity

In some drilling or completion fluid systems, polymers may be the sole viscofier. In order for a
polymer to impact viscous characteristics into a solution, chemical interactions must occur. These
include polymer-polymer, polymer-water or polymer-solids interactions. Polymer-solids
interactions are discussed later, in the section on flocculation and extenders.

Viscofying polymers are usually anionic, high molecular weight molecules. When added to a
solution, water molecules hydrogen bond to available sites along the polymer chain. This may
happen after dissociation of sodium or other ions from a functional site. The polymer begins to
extend or stretch out when sites of like charge begin to mutually repel (Figure 5.16). As the
molecule hydrates, the solution's resistance to flow increases. Structured or crystalline water may
surround the molecule contributing to further viscosity.

The chances of the polymer molecules interacting with each other, or with other components of
the system are increased if the molecules in solution are longer or higher in molecular weight.
This is seen in Figure 5.17 for two chemically identical polymers, differing only in molecular
weight. The low molecular weight polymer is about 6010
3
and the higher molecular weight
polymer is about 20010
3
, or about three times longer. The higher the molecular weight, the fewer
molecules are required to obtain a given viscosity. Since the polymer costs on a weight basis are
essentially the same, the higher molecular weight type is used to increase viscosity.
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Figure 5.16:

A . U n h y d r a t e d a ni o n ic p o ly m e r
N a
+
N a
+
N a
+
N a
+
N a
+
N a
+
H
O
H
N a
+
H
O
H
H
O
H
H
O
H
H
O
H
P a r i t i al l y h y d r a t e d
F u ll y h y d r a t e d w i t h a
c r y s t a ll in e la y e r o f w a t e r
H O
H
H
O
H
H
O
H
H
O
H
H
O
H
H
O
H
H
O
H
H
O
H
H
O
H


Figure 5.17: Viscsity of HEC polymers against concentration of 2 different MW



A non-linear relationship usually exists between the concentration of a given polymer and the
viscous properties it imparts. A typical curve relating the concentration of HEC to viscosity is
given in Figure 5.17. This shows how the viscous properties of HEC are built up slowly at low
concentrations. Initially there are insufficient molecules for them to interact with each other.
Eventually a concentration is reached when there are enough molecules in solution to ensure
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entanglement and the viscosity increases very rapidly. The initial slow response to a change in
properties as the concentration is increased is often observed in drilling fluid formulation. Care
must be taken not to over treat during this slow response stage.

Mixing different polymer types may increase polymer-polymer interactions. The resulting viscosity
may be greater than the sum of the viscosities of the two systems. This is termed a synergistic
effect and is observed for a number of polymer systems, including Guar Gum and Xanthan Gum.

Any factor that causes the polymer molecule to shrink or coil up will also reduce the viscosity of
the solution. It was shown earlier that the shape of a polymer molecule, which contained ionized
groups, would change to a collapsed coil in higher concentrations of salt. This reduction in size
also reduces the viscosity.

Not all polymers have salt sensitive viscous properties. Non-ionic polymers such as Hydroxyethyl
Cellulose (HEC) or Guar Gum will not exhibit these effects. This is also true for Xanthan Gum,
due to its rigid helical structure. When divalent cations are added to a polymer fluid system, the
effect may be rapid precipitation or loss of solubility due to crosslinking. Both result in a
viscosity reduction.

After polymerization, Cellulose polymer is partially neutralized by the addition of NaOH to form
sodium carboxylate groups (COO
-
Na
+
). When the polymer is placed in solution, it becomes
soluble due to the ionization of these groups. However, if the pH of the solution is adjusted to an
alkaline level, greater solubility will be attained as more ionized sites on the polymer chain are
formed. If the alkalinity is lowered, a reduction in the number of these sites can reduce the
viscosity.


5.4.2 Fluid Loss Control

The polymers used to reduce the fluid loss in Drilling fluids are generally anionic, straight chain,
and of moderately high molecular weight. Fluid loss reduction is achieved by three mechanisms;
some polymers enhance or contribute to all three:

1. Plugging or blocking pores.
2. Increasing fluid phase viscosity
3. Deflocculating clays.

The polymer molecule itself may cause blockage of a pore throat if the throat is small enough
(about one micron or less). For this process to occur, the polymer must not be completely soluble.
Starch and asphalt derivatives can function in this manner. Polymers may also contribute to pore
throat blockage by adhering to suspended colloidal particles such as clays and effectively
increasing their diameter.

Fluid loss reduction may also be achieved if the viscosity of the solution is increased. This effect
relates to Darcy's Law and is explained in the chapter on Fluid Loss. Polymers, which contribute
to this effect, are in the high molecular weight category. They include Guar and Xanthan Gum,
HEC, and high-viscosity Cellulose polymers. If these polymers are ionic, they may also act as a
bridge between clay particles. This promotes increased blockage through larger particle size.

Anionic polymers promote the dissociation or deflocculation of suspended solids. This results in
closer packing of cake forming materials, especially clays, reducing the filtration rate. This
process is discussed in the chapter on Clay Chemistry. Figure 5.18 illustrates this effect. The
anionic charge density and molecular weight of the polymer dictates its effectiveness as a
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deflocculant. Lignosulfonates, low molecular weight Cellulose derivatives, and Polyacrylates are
the most effective.

Figure 5.18: Fluid loss in a flocculated (left) and a deflocculated (right) system



As the environment of a fluid changes, limitations are placed on the selection of fluid loss
additives. Limiting conditions include pH, salinity, hardness and temperature. As these conditions
become more adverse, it becomes necessary to reduce the molecular weight, reduce the
(anionic) charge density, or eliminate polymers containing an acetyl linkage.

In fresh water solutions, cellulose derivatives may be used to complement the fluid loss reducing
effect of clays. As salinity or hardness increases, highly substituted Cellulose (PAC) or starch
may be used. Starch, being nonionic is best in saturated salt systems. Guar is effective in calcium
environments.

In oil based environments Gilsonite HT is used to reduce whole mud losses. Gilsonite is a coal /
asphaltenic material that is pulverized to various mesh sizes to help in pore blocking.

As the wellbore temperature increases, consideration must be directed to polymer performance
with respect to fluid loss, especially under dynamic conditions.
Starch and Starch derivatives are usually effective to 100 C;
Cellulose derivatives and Biopolymers may remain stable for short periods at up to 140
C;
Above 140 C, Acrylate or Acrylamide products are necessary;
Above 200 C, Vinylsulfonate or Vinylamide polymers should be used.

The temperature limitations of polymers are not always sharply defined and other factors must
also be considered. For example CMC may lose its viscosification characteristics at temperatures
far lower than its maximum fluid loss stability temperature. Polyacrylate may lose its effectiveness
at relatively low temperatures if calcium concentrations are high.

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5.4.3 Shale Stabilization

The term shale stabilization usually refers to a mechanism which retards the water adsorption
and the subsequent swelling / dispersion process common to most shales and clays. Most
polymers available to our industry are able to, and have been used to, stabilize shales to some
degree. This includes Cellulose derivatives, Xanthan Gum, Starch, Lignosulfonates and even
nonionic types such as HEC.

Several methods are commonly used to determine or compare the performance of various
polymers on different shales. However, the actual mechanisms contributing to this effect are still
mainly theoretical.

Descriptions of these mechanisms include: lowering the fluid's erosive action through friction
reduction, polymer adsorption onto the surface of the shale, and blocking resulting in slowing
base exchange and hydration. Adsorption of polymer onto the surface of shales is believed to be
the most effective method of stabilization. This adsorption is sometimes called encapsulation.
Nonionic polymers such as HEC, may adsorb into clay surfaces regardless of the surface charge.
Anionic polymers must either adsorb onto positive edge sites or link to the surface through ligand
exchange with aluminum at an edge site.

One theory suggests that hydrogen bonding occurs between the polymer and the water-wet
surface of the clay. Another very interesting theory suggests that it is possible to establish
covalent bonds between the polymer molecule and the quartz matrix typical of most clay
formations. Regardless of the actual mechanism, encapsulation is believed to be a relatively fast
process.

If the polymer chain is long enough, each molecule is able to attach to several available surface
sites. This attachment links the sites and retards layer separation. Polymers used specifically for
encapsulation purposes are usually polyacrylamides. The necessity to inhibit the hydration of
medium-hard to hard illite-containing formations prompted their development. Consideration of
this process demands a closer examination of the term encapsulation.

Even the hydrodynamic volumes of high molecular weight polymers are relatively small compared
to the surface area of cuttings. It is conceivable that actually only a partial, protective polymer
layer forms on the clay, contributing to both increased lubricity and hydration dispersion inhibition.
Shev and Perricone postulate that this partial layer, being highly hydrated is not impermeable to
water molecules. Eventually hydration and swelling occur, due to both diffusion and osmotic
pressure.
5
Therefore, for longer term borehole stability applications, the PHPA molecule should
have additional help.

The effectiveness of PHPA is usually enhanced when it is used with AVA HighPerm (an amine-
based compound) or KCl. Potassium ion diffusion and exchange with inter-layer shale cations is
probably slow relative to polymer adsorption at the borehole surface. The combination of a fast
acting polymer and a strong exchange cation would explain the excellent field results when a KCl
/ PHPA system is used.

An added benefit of any encapsulating polymer is that it impedes the dispersion of drilled cuttings
as they travel up the annulus. Highly dispersive montmorillonite-type formations are effectively
controlled with variations (extremely high molecular weight, i.e. 10 million) of PHPA, without the
benefit of KCl. The short retention time of cuttings in the annulus makes this application feasible.

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Extensive research has been conducted on the encapsulating properties of Lignosulfonates.
Debate has followed the research. Ava Drilling Fluids considers Lignosulfonates to be good
encapsulators for specific applications.


5.4.4 Flocculation and Extension

The term flocculation means an increase in the degree or number of particle associations in a
suspension (see flocculation, Chapter 4). Polymers flocculate solid particles by linking them into
large agglomerates. If the mass of linked particles becomes great enough, gravity causes them to
drop out of suspension. Stokes Law explains how this works, (Chapter 14 on Rheology).
Flocculating polymers are used to clean some Drilling fluids by causing undesirable solids to
settle. They may also be used to extend or increase the viscosifying properties of commercial
clays.

Flocculating and extending polymers are usually high molecular weight, anionic molecules, quite
similar in nature with the exception of their linear shape to the polymers used for primary
viscosification. Figure 5.11 shows how interparticulate associations are increased as clay adsorbs
bridging polymers. The performance of these polymers depends on several factors. There is an
optimum range of molecular weight 1010
6
is average. A polymer with a similar chemical
structure to a flocculant but with a lower molecular weight can act as deflocculant. Chain linearity
is important. Cross-linked polymers exhibit reduced solubility and cause a reduction in the degree
of interactions with particles by inactivating or immobilizing sections of the chain. The weight:
branching and crosslinking reduce length ratio. The charge distribution on the chain is important
in terms of solubility, chain extension and the degree of interaction with suspended particles.

Figure 5.19: Interaction between charged particles is increased when high molecular weight
anionic polymers are introduced to a suspension containing charged particles.



Polymers are used as flocculants in clear water drilling applications. Here the introduction of a
cation, usually calcium, to the suspension is necessary for the best results. In this case the
cation acts as a link between the negative face of a clay particle and the anionic polymer. As
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particles agglomerate they become massive enough to drop out of suspension, resulting in clear
fluid at the suction pit. If clay particles contain montmorillonite species, a total flocculant must be
used. These polymers work on all clay types. When montmorillonite formations are not present a
selective flocculant should be used. This is a nonionic / anionic polyacrylamide blend. Since
this polymer does not act on bentonite particles, sump fluids may be reused to make-up gel-
based systems. The concentrations of flocculating polymers in clear water drilling applications
must be monitored closely to avoid flocculating solids in the well bore. The operational aspects of
clear-water drilling fluids are discussed in chapter 8, Water-Based Fluids.

Selective flocculants may also be introduced to bentonite suspensions to enhance agglomeration
and settling of drilled solids without interfering with bentonite concentrations. This process usually
occurs in combination with centrifugation. Wide ranges of selective flocculants are available for
this purpose.

Polymer bridges are used to link bentonite particles in suspension. These polymers are termed
extenders. They improve the suspension and carrying abilities of a gel system without the further
addition of solid particles. Gel systems with good properties may be attained with less than 4%v
total solids and less than 10 kg/m
3
of bentonite. The operational aspects of extended gel systems
are also discussed in the chapter on Water-Based Fluids. The chapter on Clay Chemistry
explains how extending polymers are sometimes blended with dry Bentonite to improve its
performance.


5.4.5 Deflocculants

The term deflocculation refers to a reduction in the number of, or degree of particle associations
in a colloidal suspension. As this process occurs, the viscosity of the suspension decreases. This
is why deflocculants are sometimes called thinners. These products are always anionic and of
low molecular weight. As a result, they are adsorbed onto the positive edge sites of clay plates;
causing the plates to behave as through they were completely anionic. Thinners are used to
control rheological properties when influences such as salts, temperature or solids cause
increased viscosity. Figure 5.20 depicts the method by which thinners work.

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Figure 5.20: Low molecular weight, non-ionic polymers reduce the number and strength of clay
particle associations, thus reducing viscosity



Small molecules such as polyphosphates and short chain polyacrylates are often used to
deflocculate clay suspensions. The inter-particulate repulsive forces can be increased however, if
the molecule is physically large. This introduces a sterical factor, which physically prevents the
particles from approaching each other. Lignosulfonates are examples of such molecules. They
are more effective at keeping a system deflocculated in adverse environments such as high salt
or hardness.

Inputs into product selection are dependent on several parameters including, wellbore
temperature, and environmental restrictions, expected severity of the flocculation and the
alkalinity of the fluid system. Deflocculating polymers often exhibit synergistic effects.


5.4.6 Surfactants

Today's drilling fluids rely on polymers to perform several other functions. These may be of critical
importance in a given situation. The structure of these polymers can be complicated and often
their mechanisms are not fully understood.

Surfactants are a large family of compounds, which can perform various functions in drilling
fluids. They are sometimes called surface-active agents. They alter the properties of a fluid,
usually lowering the tension at the point of contact between two immiscible fluids or between the
fluid and solids. This means that the surfactant molecule must consist of two distinct sets of
functional groups, one on either end.

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Usually one group is polar and seeks polar substances. The polar group is soluble in water, and
is termed hydrophilic. The other end is non-polar and seeks non-polar substances. If it lacks any
affinity for water, it is termed hydrophobic and if it is soluble in oil, it is termed lipophilic. Figure
5.21 depicts a surfactant used for emulsifying water in oil.

Figure 5.21: Surfactant used for emulsifying water in oil

-
O
3
SO
An Emulsifier
-O3SO -O3SO
-O3SO
-O3SO
-O3SO -O3SO
-O3SO
-O3SO -O3SO
-O3SO
Oil
Oil
H
2
O
Hydrophobic tail, "oil lover"
Hydrophilic Head
"water lover"
A water in oil emulsion

Surfactants can be formulated to act at the following interfaces:

1. Air / water:
Foamers
Defoamers

2. Water / Steel:
Corrosion inhibitors
Lubricants
Detergents

3. Oil / Water:
Direct emulsions
Invert emulsions

4. Clay / Water:
Dispersants

5. Oil / Clay:
Oil wetting compounds

6. Steel / Clay:
Detergents

Surfactants may be classified by their overall net charge after solvation and dissociation of groups
or parts. That is, they are non-ionic, cationic or anionic.
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Non-ionic surfactants can be long chain polymers. These can limit the expansion of clays by
competing with water for adsorption sites on clay surfaces. Other non-ionic products are
adsorbed at oil-water interfaces. These contain lipophilic and hydrophilic groups. They are
commonly used as emulsifiers. They lower the energy (shear) and temperature required to make
an emulsion stable. They can be synthesized from alcohol anhydrides and ethylene to suit
specific applications. The chemical nature of the two chains and the HLB number determine how
they will perform. The HLB number expresses the hydrophilic: lipophilic ratio by weight. The
higher is the ratio, the more water-soluble is the molecule. Figure 5.13 depicts an anionic
surfactant acting as a water-in-oil emulsifier.

Table 5.5: Different application according to HLB ratio

HLB range Application
3 6 Water in Oil emulsifier
7 9 Wetting agent
8 15 Oil in Water emulsifier
13 15 Detergent
15 18 Solubilizer

Table 5.6: Water solubility according to HLB ratio

HLB range Water solubility
1 4 No dispersability
3 6 Poor dispersion
6 8 Milky dispersion after vigorous agitation
8 10 Stable milky dispersion
10 13 Translucent to clear solution
> 13 Clear solution

Cationic surfactants are electrostatically attracted to the negatively charged surfaces of clays
and other minerals. They are usually the salt of a fatty acid amine or polyamine. A solvated,
dissociated molecule may consist of a large organic / cationic group and a small inorganic /
anionic group.

Anionic surfactants dissociate into a large organic / anionic group and a simple inorganic cation.
The best example is soap such as sodium oleate (fig 5.22).

Figure 5.22: Sodium oleate

O
O
-
Na
+


These are able to adsorb onto the positive edge sites of clays and at water / oil interfaces.

Surfactants are often blended to accomplish more than one purpose. For example, a spotting
fluid should oil-wet the pipe and dehydrate the filter cake. Other surfactants perform more than
one function, such as when an emulsifier also acts as an oil wetting agent.


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5.5 POLYMER DESCRIPTIONS

The following text examines some of the common types of polymers used in Drilling fluids today.
It is by no means a complete list, but it should serve to provide some interesting general
information on polymers. The discussion includes, how some polymers are manufactured, the
ability of a single type of polymer to serve more than one function, and how they are altered to
diversify their functions or extend their limitations in a fluid environment.

Although many variations of polymers exist, the types considered in-depth here include Cellulose,
Xanthan Gum and Lignin-type natural or modified polymers and, Acrylate and Acrylamide
synthetic polymers.


5.5.1 Starch and Modified Starch

Starch was the first polymer to be used in any significant qualities in drilling fluids. Although
starch may impart various properties, its primary use is for fluid loss reduction. It is the principal
component of the seeds of cereal grains such as corn, wheat and rice and of tubers such as
potato and tapioca.

Figure 5.23: Potato cell



Starch grains (figure 5.23) consist of a tough outer cell wall made of amylopectin, surrounding a
substance know as amylose. Both are polysaccharide-type carbohydrates. Amylose consists of
straight chains of glucose residues ranging in molecular weight from 1010
3
to 10010
3
. The major
component, amylopectin has a molecular weight of 4010
3
to 10010
3
and is comprised of
branched molecules.

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Figure 5.24:


Processing (fig 5.24) involves rupturing the cell wall and the expansion of the amylose under the
combined influence of heat and chemical treatment such as acids and peroxides. This process is
called pre-gelatinization and produces a water dispersible product. A temperature stable grade
of starch may be prepared by cross-linking. Potato starch is usually a superior product due to its
low levels of fat and protein. Production includes a drying stage, which uses a heated drum,
producing products that exhibit higher temperature stability. Corn produces acceptable products
and is cheaper than potato starch. Wheat starch is a less acceptable product due to the high
protein content, leading to foam problems and lower biological stability.

Starch disperses in water to form colloidal, essentially nonionic low viscosity particles which plug
the pores in the filter cake. The product has excellent application as a fluid loss additive in salty
systems, particularly in salt saturated systems and hard brines. Starch products are subject to
degradation caused by bacteria, mold and yeast. In systems where the pH is less than 12 or
where salt saturation has not been reached a biocide should be added along with the starch. The
rate of bacterial decomposition is reduced if the system temperature is either very cold or above
70 C.

Most starch products are also subject to thermal degradation at temperatures above 90 C and
to shear degradation to a degree. Starch is precipitated with calcium at higher pH levels. Besides
the cross-linking to increase temperature stabilization, starch products may be modified to include
a biocide. They may also be designed to contribute to more desirable (reduced) rheological
properties, or to aid in inhibiting shale dispersion. Cationic starch products reduce the fluid loss in
lime / chloride fluids where normal pre-gelatinized starch will not.


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5.5.2 CMC and PAC

Cellulose derivatives are the most widely used organic polymers. Sodium carboxymethyl
cellulose is a non-toxic, colorless, odorless powder. Since it does not normally ferment, it is more
cost effective than starch if hard brines or salt saturated fluids are not being used. One of the
important variables in CMC products is polymer chain length or degree of polymerization (DP).
This can be varied over a wide range by the choice of cellulose source. Cotton linters are used for
long chain viscosity products. Medium and low viscosity varieties used for filtrate reduction use
wood pulp cellulose, perhaps using chemicals to de-polymerize the cellulose. The DP of these
ranges from 500 to 2000.

This semi-synthetic polymer is produced by the reaction of chloro-acetic acid on caustic soda
treated cellulose to form carboxymethyl cellulose (CMC). Cellulose is first treated with aqueous
caustic soda solution to form "alkali cellulose". The second stage is the reaction of chloro-acetic
acid with the alkali cellulose to form CMC with the structure (fig 5.8). The by-products of the
reaction are salt and sodium glycolate. The salt is removed by washing to form a pure grade (up
to 99%) product. Technical grades are usually in the order of 80% pure Na
+
CMC.

Figure 5.8: CMC monomeric unit

OH
OH
O
O
O
O
O
OH
O
OH
O
O
Na
+-
O
O
-
Na
+
O
Substituted Monomeric unit


There are three potential reaction sites (hydroxyl groups) on each CMC glucose unit. An
important variable is the number of hydroxyl groups that have reacted with CH
3
COO
-
Na
+
, or the
degree of substitution (DS). The maximum DS is 3 but an average value of 0.45 will produce a
water-soluble product. The higher the DS, the greater the solubility and ability to retain water
within its structure and hence exhibit improved fluid loss control properties. Drilling fluid CMC has
a DS of about 0.8.
Products with higher levels of DS about 1.0 are called polyanionic cellulose (PAC). CMCs
with higher DS values require higher levels of reagent. This also increases the residual salt
content such that some degree of purification or salt removal may be required. Both these
aspects increase the cost of production. However, the stability of the molecule to salt is also
improved. This is clearly shown in Figure 5.25 where the viscosities two CMCs with different DS
values are given as a function of the NaCl content. The viscosity of the more highly substituted
polymer is essentially stable to the effects of the salt.
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Figure 5.25: Effect of increasing DS in CMC on the viscosity as salt concentration is raised.



The three main variables, molecular weight, degree of substitution, and purity or salt content,
generate a wide range of products, which have a number of diverse applications. CMC is an
anionic polymer that adsorbs onto clays. The length of the solvated molecule may be affected by
the degree of substitution and salt concentration. Low viscosity types are used to lower fluid loss
in fresh water, bentonite-based systems, and in saline conditions up to saturation. The molecule
may exhibit deflocculation effects especially in flocculated systems, as it has a low molecular size
and increases the net negative charge on the clay particles. Low viscosity CMC may be sold
either purified or unpurified (CMC LVP, CMC LVS, CMC LVT).

High viscosity types are used to develop shear thinning characteristics in water-based fluids.
They also control fluid loss effectively at low concentrations, especially the higher molecular
weight varieties. The apparent viscosities of CMC suspensions are high at low shear rates. The
viscosity of CMC suspensions decreases substantially with temperature. High viscosity CMC may
be sold either purified or unpurified (CMC HVP, CMC HVS, CMC HVT).
Thermal degradation of CMC begins to accelerate rapidly at temperatures above 140 C.

The anionic CMC molecules are susceptible to form insoluble complexes with polyvalent cations
such as calcium or aluminum. The potential for these problems is reduced in the more highly
substituted PAC types. CMC can be used in lime-based systems if the calcium level is reduced to
below 500 mg/l. The high viscosity grades of PAC posses inhibitive properties when used in
sufficiently high concentrations, due to the adsorption of the polymer on the solids.
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5.5.3 HEC

Hydroxyethyl cellulose is a nonionic, cellulose-based polymer. It has a specific application as a
viscofier in solids-free completion brines. HEC is a linear molecule, which may be up to two
microns in length. In solution it forms a random coil, such that its effective length is about 20% of
its molecular length.

The coil shape provides good viscosity characteristics. Since it is flexible, it becomes elongated
when in motion. This contributes to well-developed shear thinning qualities in an HEC solution.
HEC exhibits some filtrate reducing characteristics, but is not normally used in Drilling fluids
because it exhibits no thixotropic properties. Figure 5.26 shows the HEC molecule and its
acetyl linkage. HEC is the most acid soluble, least damaging viscofying polymer explaining its
wide use in completion brines.

It is non-ionic so its dimensions do not change in the presence of electrolytes, making it
relatively stable in most moderate, basic environments. HEC does have both shear and
temperature limitations, although magnesium oxide may stabilize HEC, enabling it to perform at
temperatures as high as 130 C. HEC has a tendency to foam when mixing.

Figure 5.26:



The production process is based on the reaction between alkali cellulose and ethylene oxide to
produce molecules with the structure shown in Figure 5.26. The first reaction is with the hydroxyl
groups of the cellulose to attain water solubility. The degree of substitution is controlled at range
of 0.9 1.0. The ethylene oxide may also react with the substituted chains. The level of "molar
substitution" refers to the total number of moles of ethylene oxide per cellulose unit. It usually
ranges from 1.8 2.0.

The molecular weight, degree of substitution, extent of molar substitution, and the uniformity of
substitution all contribute to the net effect of the polymer. HEC is used in concentrations of 0.6 to
6.0 kg/m
3
.

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A derivative product, CMHEC is made by the sequential treatment of alkali cellulose with chloro-
acetic acid followed by ethylene oxide. The degree of substitution of CMC groups is in the low
range of 0.6 0.8. This initial treatment opens up the cellulose chains so the successive ethylene
oxide treatment is carried out uniformly on the molecule to a molar substitution level of 0.3 1.6.
The uniform distribution of the anionic groups renders the molecule much more resistant to the
precipitation effects of multivalent ions such as calcium. The product is relatively expensive
because it is processed twice, but has found application in more extreme environments including
high temperatures and hard brines. CMHEC is used as a fluid loss reducer and retarder in oil well
cement slurries.


5.5.4 Guar Gum

Guar Gum is a natural, essentially non-ionic polymer that has an excellent application as a
viscofier for spud-in fluids, that is, short duration fluids. Guar solutions hydrate readily, exhibiting
shear thinning character and insensitivity to salts and various multivalent ions. Guar Gum is
sometimes used in low concentrations to flocculate drilled solids and guar derivatives have been
used for viscosification in solids free-workover fluids. Guar also exhibits limited filtrate reduction
and wellbore stabilization characteristics.

Guar is derived from the seeds of the guar plant, cultivated in India, Pakistan and Texas. The
plant develops pods, each of which contains five or six seeds. The seeds undergo a multistage
process of grinding and sifting to separate the guar containing endosperm from the outer hull and
the germ. The result is a polysaccharide consisting of a linear backbone of polymannose,
substituted at every other unit by a short galactose branch. This is illustrated in Figure 5.27.

Figure 5.27: Guar Gum structure



The mannose units are linked to each other by means of glycosidic bonds. The molecular weight
of guar is in the order of 2010
3
. Note that each repeating unit has 9 potentially reactive OH
groups, able to form guar derivatives. Usually the derivatives have the same basic structure as
guar. Chemical treatments to guar produce variations, which are more biologically and thermally
stable. Additives can be incorporated into the formulation to improve its ability to disperse. Cross-
linking with borax is sometimes used to increase its viscosification characteristics.

Viscosification is accomplished by the normal association and hindrance mechanisms. Structured
water in the vicinity of the molecule augments this. Guar Gum is prone to bacterial degradation
unless protected by either a biocide or high salinity or pH. However, high pH and hardness
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together may inhibit the dispersion of guar or initiate its precipitation through cross-linking.
Normally guar degrades rapidly at temperatures above 60 C, limiting its use to shallow wells.

Thermal degradation is a permanent loss in viscosity due to cleavage of the acetyl bond,
resulting in depolymerization and is not merely a temperature-thinning phenomenon.


5.5.5 Xanthan Gum

Xanthan Gum (XC polymer), is an anionic, water-soluble polysaccharide biopolymer. It is
produced by the action of the bacteria Xanthomonas Campestris on carbohydrates. It is classified
as a natural polymer, although it is actually processed. It has been used as a viscofier and
suspending agent in fresh or salt-water solutions since the middle 1960s. Its superior cleaning,
shear thinning and suspension properties at low concentrations, combined with its stability in
saline environments, make it very cost effective. It has a particular application in remote locations
where transportation costs are high, and in fact, it is the sole viscofier in certain Arctic and
Offshore applications. The polymer also functions as a fluid loss control agent in that its molecular
size contributes to a filter cake plugging effect. It is compatible with other filtrate reducers such as
bentonite and CMC. Xanthan Gum has desirable properties for workover and completion
applications.

Xanthan Gum (fig 5.28) is extracted as the polysaccharide formed as a coating on each
bacterium. The bacteria are grown under aerobic conditions with a suitable source of
carbohydrate such as sugar solution and minerals. Fermentation conditions are carefully
controlled. The viscosity increases to a point where the bacteria are precipitated with isopropyl
alcohol before being, filtered, washed, dried and milled.

Figure 5.28: Xanthan gum biopolymer structure




The major sugars are D-glucose, D-mannose, D-glucuronic acid. The monomer consists of a
linear backbone of glucose residues linked with D-mannose, D-glucuronic acid residues which
have a 3 unit long side chain attached to them. The carboxyl groups on the side chains make the
polymer anionic. The result is the complex, branched or network structure, shown above. The
polymer chains associate to form a double helix as shown in Figure 5.29 and Figure 5.30. The
interacting polymer chains form a rod-like molecule with a molecular weight of about 20 million
and dimensions of about 2 10 microns long and 0.2 0.6 microns in diameter.

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Figure 5.29: XC polymer network



Variations on the effect of Xanthan Gum may be attained if it is cross-linked with various
chromium compounds. The viscosification characteristics of Xanthan can behave in a synergistic
manner with other polymers such as CMC, HEC and Starch.

Figure 5.30: Helical structure of Xanthan Gum



At low shear rates, the molecules form a complex, aggregate network through hydrogen bonding
and entanglement. This network accounts for the polymer's viscosity and suspension properties.
Shear thinning (see the chapter on Rheology) results from the disaggregation of this network and
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alignment of individual polymer molecules in the direction of the shearing force (fig 5.31). The
rigid, helical structure ensures that the molecular dimensions do not change excessively with
increasing salt concentrations.

Figure 5.31: Effect of shear on XC polymer network



Although the viscous properties of Xanthan Gum are not affected by salt or moderate
temperatures, several other influences can be detrimental to its performance. In the presence of
divalent cations and high pH (an environment encountered when drilling green cement) it can be
precipitated. It is also subject to degradation by microorganisms and enzymes. Therefore, when
it is used to make up kill mud the pH should be maintained above 11.0. In packer fluid
applications, a biocide should be used. Thermal degradation of Xanthan Gum begins at around
75 C.


5.5.6 Scleroglucan

Scleroglucan is a non-ionic, water-soluble biopolymer produced through fermentation. Aqueous
solutions of scleroglucan exhibit exceptional shear-thinning rheology and good suspending ability.
The advantages of scleroglucan in comparison to other biopolymers are higher thermal stability,
pH stability and tolerance of divalent cations such as Ca
++
/ Mg
++
. Scleroglucan shows much
higher thermal stability than Xanthan gum and can be used up to 140 C (285 F) whereas
Xanthan gum shows a gradual viscosity decrease starting at 70 C (155 F). pH does not
influence the performance of scleroglucan over a broad range from pH 1 to 12.
Scleroglucan is a regularly branched polysaccharide of the scleroglucan type (see fig. 5.32). It is
produced through aerobic fermentation of a carbohydrate by a fungus filamentum: its molecular
weight is about 50010
3
.
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Figure 5.32: Scleroglucan structure



In an aqueous solution, three of these scleroglucan molecules adopt a triple-helical conformation
and can be described as rigid rods. Under static conditions, these rods form a web-like structure.
The resulting gel provides excellent carrying capacity. As scleroglucan is non-ionic, it tolerates
high amounts of mono-, di- and tri-valent cations like Na
+
, K
+
, Ca
++
, Mg
++
, and Fe
+++
.

Characteristics of scleroglucan include:
high low shear rheology
thermally stable up to 285 F (140 C)
stable at pH 1 to 12
completely tolerant to NaCl, NaBr and KCl
tolerant to high calcium levels
compatible with common drilling fluid and cement additives
non-damaging to the formation
environmentally safe

Scleroglucan is used in concentrations of 0.5 to 5 ppb (1.5 15 kg/m
3
) depending on application.
In long-term fresh water applications at temperatures below 80 C (175 F) the addition of a
biocide is recommended to preserve the biopolymer. In brine applications it is recommended to
disperse scleroglucan first in lower density brine and then add salt to the required density. The
heat developed during the salt addition will greatly enhance the hydration of scleroglucan.
Scleroglucan shows fastest solubility at or above 60 C (140 F). Scleroglucan provides an
exceptional shear-thinning (visco-elastic) rheology with high yield point, low plastic viscosity and
high low-end readings. The result is excellent static and dynamic carrying capacity with low pump
pressure being sufficient to move the fluid.

Typical fluid systems for which scleroglucan can be used include:
fresh and seawater mud
lime and gypsum mud
salt saturated mud
silicate mud
CaCl
2
and CaBr
2
brines
K-formate brines
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Low-bentonite mud

5.5.7 Lignosulfonates

Lignosulfonates and chrome Lignosulfonates (CLS) are strongly anionic by-products of the sulfite
process used to separate cellulose pulp from wood. They are the most widely used
deflocculants in water-based Drilling fluids. Deflocculating a clay suspension, results in a cost-
effective reduction in fluid loss and cake thickness. This is discussed in the Fluid Loss, Chapter 6
and the Clay Chemistry, Chapter 4. Lignosulfonate products are often used to augment primary
fluid loss reduction products. Lignosulfonates have the ability to stabilize oil-in-water emulsions.
The absorption of Lignosulfonate on clay surfaces reduces swelling and cleavage, promoting hole
stabilization and the recovery of un-dispersed cuttings.

Figure 5.33: Lignin and lignosulfonate polymers derive from hydration of sugars to give aromatic
(phenol-type) compounds

OH
HO
OH
O
O
OH
OH
HO
O O


Lignosulfonate contains complex structures that include aromatic (phenol) rings and acid
groups. Lignins are formed by the removal of water from sugars to afford aromatic structure
Figure 5.21. Browning
6
postulated that the structure was a ridged ellipsoid from which short
chains containing sulfonic and hydroxyl groups protrude. The structure of the molecule is tight
which minimizes swelling tendencies. It is hydrophilic and capable of hydrogen bonding.
Molecular weights vary from 1000 to 20000. Manufacturing process variables and the choice of
reagents have led to numerous patents and many Lignosulfonate products. Common generic
types include calcium, chrome, ferro-chrome and chrome-free products.

The deflocculation mechanisms stem from the adsorption of the non-ionic lignosulfonate
micelles onto the positive edges of clay particles. This results in encapsulation if the
concentration is high enough. The emulsion stabilization mechanism is derived from adsorption at
the oil-water interface.

The sulfonate groups provide stability to most types of ionic contamination. Thermal degradation
usually begins to affect deflocculation properties at about 120 C. The thermal degradation or
biodegradation of chrome Lignosulfonates can contribute to the formation of CO
2
and H
2
S,
however, the addition of chromate increases its temperature stability. Adding sodium hydroxide
increases the solubility of all lignosulfonate products.


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5.5.8 Polyacrylamide

Partially Hydrolyzed Polyacrylamide (PHPA) polymers are synthetic, anionic, acrylamide /
sodium-acrylate co-polymers. These polymers have been used successfully throughout the world
to aid in the maintenance of borehole stability by encapsulating or surrounding hydratable shales.
This encapsulation effect can also contribute to a reduction in overall drilling costs by eliminating
sloughing and reducing the tendency of drilled cuttings to disperse in the annulus. This promotes
increased solids control efficiency, a reduction in lost time due to mud-rings, and less tendency
towards bit-balling. PHPA is also used as a clear-water drilling flocculant. The lubricating
properties of PHPA polymers have been well documented.

Polymerizing acrylamide monomers in acrylic acid makes PHPA. The acid converts some of the
amides on the acrylamide chain to carboxylates. This process is called hydrolysis (mentioned in
section 4.2). Figure 5.34 shows an acrylamide acrylate co-polymer. The degree of hydrolysis
imparted to a PHPA molecule depends on the specific function it is required to perform.
A 30% hydrolyzed PHPA contributes to hole stability;
A 10% hydrolyzed molecule contributes to water clarification by flocculation;
A 70% hydrolyzed molecule contributes to filtration control.

The structure of PHPA is generally linear although cross-linking is possible. Molecular weights
vary but are usually extremely high. Some of the best PHPA polymers include the Alcomer series.

Figure 5.34: PHPA acid structure

O NH
2
OH O NH
2
O
n


The encapsulation mechanisms of PHPA are believed to be either attraction of the molecule to
positive, clay edge sites and / or hydrogen bonding. The reason the 30% hydrolyzed PHPA
provides the best inhibition characteristics are believed to be because the charged sites on the
chain match the general spacing of the clay plates. In the case of reduction in bit balling, the
mechanism is thought to be due to the attraction of the cationic amide groups to the steel surface
of the string and bit.

The carbon link in all synthetic polymers, including PHPA renders them both, thermally and
biologically stable. Excessive concentrations of multi-valent cations, such as calcium,
magnesium and aluminum do affect PHPA performance. When drilling through soluble anhydrite
(CaSO
4
) the volume of sediment in the standard PHPA floc test begins diminishing at 200 300
mg/l of total filtrate hardness. The assumption that the test has been affected, and the polymer
remains functional is incorrect. The polymer is actually coiled up as in Figure 5.34 and is
effectively useless.

Polyacrylamide polymers can be susceptible to oxidative degradation at higher temperatures,
especially in the presence of metal ions and acidic conditions. The shear degradation mentioned
earlier in the chapter is usually only noticeable after prolonged rates of excessive shear, such as
when a batch is left standing in a chemical barrel with a high-speed electric agitator running.

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5.5.9 Polyacrylates

Polyacrylates are non-ionic synthetic polymers used to control fluid loss and deflocculate clays
at moderately high temperatures. Higher molecular weight varieties are able to extend bentonite
and flocculate as shown in Table 5.7. Very low molecular weight polyacrylates are used in the
formulation of scale inhibition products.


TABLE 5.7 Relationship between molecular weight and function for polyacrylate

FUNCTION MOLECULAR WEIGHT (x 10
3
) NUMBER OF MONOMERS (x 10
3
)
Deflocculant 7 1
Fluid Loss Additive 6 8
Flocculant 3000 40
Bentonite Extender 10000 14

Polymerization occurs in an aqueous solution, beginning with a vinyl monomer. The molecular
shape is believed to be linear. Figure 5.34 depicts the structure of polyacrylate. The molecular
weight can vary substantially.

The carbon-carbon backbone of this group makes them resistant to temperature to 200C, and
to bacterial degradation. They can also have a synergistic effect with lignosulfonates. The first
polyacrylate products were highly sensitive to high hardness levels. However, recent
modifications have enabled them to be used in seawater systems and where anhydrite is
common.

Figure 5.34: n-polyacrylic acid

O OH OH O OH O
n



5.5.10 Polyalkylene glycols

The sudden onset of turbidity of a non-ionic surfactant solution on raising the temperature is
called cloud point. At somewhat higher temperature the solution begins to separate into 2
phases: one is an aqueous solution containing monomolecular dispersed species of surfactant
without micellar aggregates; the other is a phase rich in non-ionic surfactant with solubilizate and
water dissolved in it. The presence of a solubilizate affects the cloud point and the phase-
separation temperature. The cloud point phenomenon of polyalkylene glycols is due to the
formation of giant micelles: when they become very large, the turbidity (cloud point) becomes
perceptible even to the naked eye. The hydration of ether oxygens of polyoxyethylene group is
the main factor in keeping the non-ionic surfactant in solution. The increase of temperature
causes partial dehydration and finally results in the separation of the surfactant-rich phase.
Non-ionic surfactants having a longer polyoxyethylene group show a higher cloud point by virtue
of a greater capacity to hydrate. The cloud point is rather insensitive to the concentration of
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surfactant itself, but is appreciably influenced by the presence of certain additives: electrolytes
suppress the cloud point in proportion to their concentration.
The onset of clouding in drilling fluids has been associated with increased lubricity, a reduction in
fluid loss, and an increase in shale stabilization. The cloud point phenomenon has been exploited
to produce thermally activated fluids where the mud composition is formulated to give glycol
separation at the drill bit or lower well bore region, the glycol re-dissolving in the cooler upper
sections of the well.


5.5.11 Descriptions of other Polymers

The following text describes other drilling fluid polymers, which are less common than the ones
previously discussed. They are by no means less important. As drilling conditions become
increasingly adverse with respect to temperature and abnormal formation pressures, some of
these products are becoming much more common.

Lignin or lignite is used extensively in many areas as a deflocculant and fluid loss reducer.
Lignite products are natural, anionic, long-chain molecules similar to Lignosulfonates. Leonardite,
a low-grade coal is the lignitic material used in Drilling fluids. Lignite has the ability to reduce fluid
loss, stabilize emulsions and stabilize fluid properties against the effects of high temperatures.
Lignite may be modified using reagents such as Sodium Hydroxide (causticized lignite).
Unmodified lignite is not as effective in calcium-contaminated or saline fluids.

Sodium Polyphosphates are large anionic, synthetic molecules used mainly as thinners. They
are produced by heating orthophosphates and removing the water or by melting the anhydrous
components together. The product is then ground. Sodium acid pyrophosphate or SAPP
(Na
2
H
2
P
2
O
7
) is the most common type. Figure 4.26 shows a polyphosphate molecule associating
with a positive clay edge. Its acidic nature makes it effective in treating cement contamination by
reducing pH. It also precipitates calcium. Polyphosphates are not as effective in saline
environments above 10000 mg/l Cl
-
. High temperature applications are limited also, due to their
revision back to flocculating orthophosphates prior to reaching 100 C. SAPP is sometimes used
on shallow land wells to prevent "mud rings" See the chapter 8, Water-Based fluids.

VSVA (vinylsulfate / vinylamide) polymers are becoming increasingly common as wellbore
temperature conditions become more adverse. VSVA is an anionic synthetic co-polymer, which in
some cases actually works better as the Drilling fluid environment gets worse. The main function
of VSVA is filtrate reduction. The API filtrate test does not always provide an accurate indication
of temperature-induced changes to fluid loss values. HTHP values however, may noticeably
increase at temperatures of 100 C or more, depending on the fluid system and products being
used.

VSVA polymers have a molecular weight of 1 2 million. This provides moderate viscosification
properties a secondary function. The vinyl backbone and carbon-carbon bonds make it stable to
over 200 C. The sulfonate groups provide a strong charge density, allowing the polymer to be
extremely tolerant to multivalent cations and also to function as a rheological stabilizer. VSVA
polymers are tolerant to moderate solids concentrations and are able to stabilize sensitive shales
to a degree.

SSMA (Sulfonated Styrene Maleic Anhydride) is a short-chain synthetic co-polymer. It is a
deflocculant used in solids-laden fluids where temperatures are high enough to limit the use of
Lignosulfonates, Lignites and Polyacrylates. The carbon-carbon bonds make it stable to 260 C.
The sulfonate groups render it effective in electrolytic environments where Polyacrylaltes fail. This
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polymer is especially applicable in cement-contaminated systems where deflocculation is
essential, especially in hot holes.


Figure 5.35: Sulfonated styrene maleic anhydride (SSMA)

SO
2
O
-
Na
+
O
O
O
-
Na
+
O
-
Na
+



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REFERENCES

1 Fred W. Billmyre Jr., Textbook of Polymer Science 2nd ed. (New York: John Wiley
E. and Sons, 1971), 5; all subsequent citations are to this edition.

2 Darley and Grey, Composition and Properties, 179.

3 Yang S. H. and Triber L. E., Chemical Stability of Polyacrylamide Under Similar Field
Conditions. SPE paper 14232, September 1985.

4 Billmyre, Polymer Science , 24.

5 Jim J. Sheu and Charles Perricone, Design and Synthesis of Shale Stabilizing
Polymers for Water Based Drilling fluids. SPE paper 18033.

6 Browning, Lignosulfonate, Stabilized Emulsions in Oil Well Drilling fluids, JPT, June
1955.
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CHAPTER 6

FLUID LOSS CONTROL


6.1 KEY POINTS & SUMMARY

6.2 STATIC FILTRATION
6.2.1 Darcy's Law
6.2.2 Static Filtration
6.2.3 Practical Static Fltration
6.2.4 The Relationship Between Filtrate Volume and Time
6.2.5 The Relationship between Filtrate Volume and Pressure.
6.2.6 Filter Cake Permeability
6.2.7 The Influence of Particle Associations on Cake Permeability
6.2.8 The Effects of Temperature

6.3 DYNAMIC FILTRATION
6.3.1 Equations for Dynamic Filtration
6.3.2 Practical Dynamic Filtration
6.2.3 Filtration beneath the Bit.

6.4 FLUID LOSS CONTROL IN WATER-BASED FLUIDS
6.4.1 Bridging Solids
6.4.2 Cake Forming Solids
6.4.3 Product Selection

6.5 FLUID LOSS CONTROL IN OIL-BASED FLUIDS
6.5.1 Cake Formation
6.5.2 Colloidal Solids
6.5.3 Formulation for High Fluid Loss
6.5.4 Comparison of Static and Dynamic Filtration Rates.

6.6 RELATIONSHIP TO HOLE PROBLEMS
6.6.1 Differential Sticking
6.6.2 Formation Damage
6.6.3 Borehole Stability



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6.1 KEY POINTS & SUMMARY

Whole fluids and filtrate lost into the formation during the course of drilling and completing a well
may have a direct effect on one or more functions of the drilling fluid. These functions include the
maintenance of borehole stability, the protection of producing formations, the reduction of friction
and the improvement of penetration rates.

Several mathematical models describe the relationship of filtrate loss to pressure, temperature
and time. However, predicting dynamic filtrate loss rates from static values is difficult. The
mechanisms of fluid loss reduction in all fluid types generally relate to the type, size and
relationship between filter cake constituents. The viscosity of the liquid phase is also a factor.

The selection of the proper combination of filtrate reducing mechanisms and additives may entail
a substantial amount of background laboratory work. The on-sight evaluation of product
performance and the implementation of well thought-out strategies can lead to a reduction in
problems associated with fluid loss.


6.2 STATIC FILTRATION

6.2.1 Darcy's Law

In the middle of the 19th century, a French engineer, H. D'arcy developed equations for the rate
of flow of water through sand filtration beds. His work was expanded to include viscosity in the
following equation:

Equation 6.1, Darcy's law:

q = k
A P
l


Where: q = the flow rate
A = the cross section area
P = the pressure differential across the filter
l = the length of the filter bed
k = a constant related to the physical character of the filter bed
= the viscosity

A filter has a permeability of one Darcy when water, with a viscosity of 1 cp, flows at a rate 1 cm
3
/
sec through an area of 1 cm
2
with a pressure gradient of 1 atmosphere per cm. The oil-field unit
is the millidarcy (md) which is equal to 10
-3
Darcy.


6.2.2 Static Filtration

In the case of static filtration, the filter cake increases in thickness as the liquid fraction is
removed by the filtration process. This leaves a filter cake containing solids and some liquid. As
the filter cake grows in thickness, the filtration rate is reduced. It can be shown by integration of a
differential from of equation 6.1, the cumulative filtrate volume as a function of time can be given
by the following equation:
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Equation 6.2

q
w
2
=
2 k P A
2



qw
qc
t

Where: q
w
= the volume of the filtrate at time t
q
c
= the volume of the filter cake (related to the thickness of the filter cake, L,
through the area of the filter cake, A)
= the viscosity of the filtrate
k = the permeability of the filter cake


6.2.3 Practical Static Filtration

Equation 6.2 can be rewritten as:
Equation 6.3:

q
w
= A C
1/2
t
1/2


Where C is a new constant incorporating the constant terms:

Equation 6.4

C =
2 k P


qw
qc


These equations predict a linear correlation between the cumulative filtrate volume and the
square root of time. These are plotted for a typical drilling fluid system in figure 6.1. The initial
part of the curve deviates from the predicted straight line because of two factors. There may be
an initial loss, termed the spurt loss. This occurs when an unrepresentative volume of filtrate,
including solids is lost through the filter medium because there are insufficient solids to block the
pores in the filter paper. The time allocated for measuring the spurt loss ceases when individual
drops begin flowing from the discharge nipple. Secondly, error is introduced in the initial stages
as the filter paper is wetted and the volume between the paper, wire mesh support and discharge
point is filled. This varies with different types of equipment and the state of dryness of the
equipment at the start of the measurement.

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Figure 6.1 Relationship between cumulative filtrate volume and time for static filtration


If the spurt loss is greater than the void volume, the extrapolated linear part of the curve in Figure
6.1 has a positive intercept in the x axis. If the spurt loss is low there may be a negative
intercept. In practice, equation 6.3 is modified to include this spurt loss, q
o
, so the equation
becomes:

Equation 6.5

q
w
- q
o
= A C
1/2
t
1/2


The standard API filtration test cells for the filtrate volume to be measured at room temperature
over a 30 minute period through a filter area of 45 cm
2
and a differential pressure of 100 psi.


6.2.4 The Relationship Between Filtrate Volume and Time

When a drilling fluid is filtered through paper at a constant temperature and pressure, the volume
of filtrate is proportional to t . This relationship may be expressed algebraically as:

Equation 6.6, Relationship between Filtrate Volume and Time:

q
2
= q
1

t
2
t
1



Where: q
1
= The recovered volume of filtrate (cm
2
)
t
1
= The time at which q
1
, was measured
t
2
= The time at which a calculated volume of filtrate is required
(usually 30 min.)
q
2
= The unknown volume of filtrate (cm
3
) at the time t
2


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The 30-minute filtrate volume may be predicted by measuring the volume at 7.5 minutes and
doubling the value, since:

30
7.5
= 2


Equation 6.6 may also be arranged to obtain a value for filtrate volume at 30 minutes, if the 30
minute time period has been exceeded.

q
30
= q
2

30
t


Where: t
=
the time the sample was recorded
q
2
= the volume of filtrate at t
1

q
30
= the volume of filtrate at 30 minutes

A factor called the zero error may be applied to these equations. This term is related to the
discrepancy in the linear relationship shown in Fig. 8.1, where the curve does not intersect the
orgin. Zero refers to the fluid loss at time zero, or the spurt loss. When correcting for spurt loss,
equation 8.6 becomes:

q
30
- q
0
= (q
30
- q
0
)
t
30

t
1


Where q
0
= the volume of spurt loss filtrate

Certain API product specifications require a fluid loss value, including bentonite, drilling starch
and CMC. When testing is conducted, the spurt loss and void volume effects are eliminated by
measuring the fluid loss between 7.5 and 30 minutes, since this is the linear part of the curve.
The volume is doubled to arrive at a valve comparable to the volume collected in 30 minutes.


6.2.5 The Relationship between Filtrate Volume and Pressure.

Equation 6.2 predicts that the accumulated volume of filtrate, Q
w
, should be proportional to the
square root of the applied pressure. A log-log plot of filtrate volume versus pressure should yield
a straight line with a slope of 0.5. This relationship is not observed for drilling fluids because the
filter cake is compressible to a degree that is dependent on the fluid type.

The cake permeability decreases as pressure increases. The relationship may be expressed as:

Equation 6.7:

q aP
x


Where x is the slope, x varies with the compressibility of the cake but is always less than 0.5.
The effect of pressure on filtration rates is a direct function of the compressibility of the cake.

Cakes formed from bentonite alone are so compressible that the slope may be zero and the
volume of filtrate is constant with respect to pressure. This is due to the shape of bentonite
particles and their tendency to align themselves parallel to the plane of pressure differential.
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Cakes formed from other clays have been found to have x exponents ranging from zero to 0.2.
When angular solids are introduced into a fluid the value of the x exponent increases. In oil-
based fluids there is an additional factor. This is the increase in the viscosity of the oil due to the
increase in pressure. This tends to reduce the expected value of the slope as the pressure is
increased.


6.2.6 Filter Cake Permeability

The permeability of the filter cake can be determined by measuring filtrate volume and cake
thickness at the end of the 30 minutes filtration period. This is not easy task due to the poor
definition of the top of the filter cake. Equation 6.2 can be rewritten as:

k =
q
w
l
2 P A t


When l is given in millimetres, then for the standard API test:

Equation 6.8:

k = q
w
l (8.95) 10
-3


As an example, for fresh water where, is 1, a 2 mm thick filter cake and a fluid loss of 10 cm
3
,
the filter cake permeability is 180 10
-3
md. Permeabilities of drilling fluid filter cakes are typically
in the range 10
-2

md to 250 10
-3
md.

Filtration tests against supports with different permeabilities have established that, the
permeability of the filter cake is the controlling factor - where the formation has a permeability of
about one millidarcy. Typical permeabilities of formations are given in Table 6.1 which shows that
the fluid loss is critical in sandstones but not in shale formations.


Table 6.1 Range of Permeabilities of Typical Formations


Formation Type


Range of permeability, millidarcies


Very Coarse sandstone

5 000 - 10 000
Good oil production 10 - 1 000
Gas production tight sandstone 0.1 - 1
Filter cake 0.002 - 0.150
Shale 0.000001

6.2.7 The Influence of Particle Associations on Cake Permeability

Colloidal particle associations in drilling fluid suspensions are discussed in the section on Clay
Chemistry. It also dicusses the influence of various flocculants on fluid loss. When a clay
suspension is flocculated it means that the degree of clay structure is increased. A loose, open
network is formed. This network persists to a degree within the cake, increasing its permeability.
In a deflocculated suspension, clay particles are free to lay flat. An overlapping, uniform
distribution pattern is created against the plane of pressure differential. Deflocculating chemicals
also serve to toughen the cake and enhance particle size distribution.
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In some cases the addition of water to the fluid may influence the nature of the particle
associations and actually reduce the fluid loss. This may result from a reduction of the net cation
concentration or as an aid to dispersion (more particles) in solids laden fluids. In a dehydrated
suspension there is competition between all constituents for free water. When water is added,
clays and polymers hydrate properly, contributing to lower fluid loss values.

Cake permeabilities of flocculated fluids may be in the order of 10
-2
md, those of untreated fresh-
water fluids in the order of 10
-3
md, and fluids treated with thinning agents, in the order of 10
-4
md.
1



6.2.8 The Effects of Temperature

The volume of filtrate varies with the square root of the viscosity of the liquid phase:

Equation 6.8:

q
2
=
q
1

viscosity
1
viscosity
2


Where:
q
2
= unknown filtrate volume at viscosity
1
(cm
3
)

q
1
= known filtrate volume at viscosity
2
(cm
3
)

Theoretically, decreasing the viscosity will increase the fluid loss. Table 6.2 shows the effect of
temperature in the viscosity of water and 6% NaCl brine. Using Equation 6.8 and Table 6.2 it can
be seen that the filtrate volume would be increased from 10 cm
3
to 14 cm
3
if the temperature
were increased from 10C to 40C in a water-based system:

14.19 = 10
1.308
0.656


Table 6.2 The Viscosity of Water and 6% Sodium Chloride Brine at Various
Temperatures


Temperature
(C)


Temperature
(F)

Viscosity water
(cp)

Viscosity Brine
(cp)
0 32 1.792 -
10 50 1.308 -
20.2 68.4 1.000 1.110
30 86 0.801 0.888
40 104 0.656 0.733
60 140 0.469 0.531
80 176 0.356 0.408
100 212 0.284 -
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Temperature
(C)


Temperature
(F)

Viscosity water
(cp)

Viscosity Brine
(cp)
140 284 0.196 -
160 320 0.174 -
180 356 0.150 -
200 392 0.134 -
220 428 0.121 -
260 500 0.1004 -
300 572 0.086 -


This viscosity relationship doesn't have a practical application for real drilling fluids. In clay
suspensions an increase in temperature can contribute to better hydration and dispersion of
commercial clays, ultimately reducing the filtrate volume.

At higher temperatures, the viscosity effect may be compounded by several factors. The
increased solubility of contaminating ions increases the effect of flocculation on cake
permeability. The thermal flocculation of suspended clays also increases filtrate volume. The
degradation of most organic filtration control additives usually begins when temperatures exceed
100C, continuing at a non-linear (increasing) rate as temperature increases.

Accurate prediction of filtrate volumes at elevated temperatures can't be made from
measurements recorded at lower temperatures. Therefore, most operators require that high
temperature, high pressure (HTHP) fluid loss and cake values be reported when static downhole
temperatures exceed 50 - 60C. Using the actual bottom-hole temperatures for testing gives the
most realistic results if establishing a trendline is required.


6.3 DYNAMIC FILTRATION

6.3.1 Equations for Dynamic Filtration

It is generally accepted that downhole filtration rates are higher under dynamic conditions than
they are under static conditions. This is because the filter cake build up is not a continual
process. At some point, it begins to become eroded by the flow of fluid past it. H. D. Outmans
equation for dynamic filtration is expressed as:

Equation 6.9 Dynamic filtration:

q =
k
1
( /f)
-v+1

l(-v+1)


Where: k
1
= the cake permeability at 1 psi
= the shear stress exerted by the fluid
f = the coefficient of internal friction of the cakes surface
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= viscosity
l = the equilibrium cake thickness
(
-v+1
) = a function of the compressibility of the cake

Experimental conditions used in laboratories have been so diverse that a critical evaluation of this
equation isn't possible. However, in general the predicted output values have been supported.
Since the thickness of the filtercake is limited by mechanical erosion, the viscosity factor may be
more important in dynamic filtration than in static filtration.


6.3.2 Practical Dynamic Filtration

Figure 6.2 depicts H.D. Outman's static and dynamic filtration and cake thickness regime in a
borehole. When the formation is first exposed there is an initial spurt loss of whole fluid until the
pores are bridged by solids. The cake then builds in thickness to an equilibrium point. During
this stage cake formation is influenced by pressure (compressibility) and the erosion and
redepositing of particles into it. When the equilibrium cake thickness and permeability is reached
the relationship between filtrate volume and time becomes linear. Studies have indicated that
the time required to reach equilibrium dynamic filtration rates vary from 2 hours to over 25 hours.


Figure 6.2 Relative static and dynamic filtration in the borehole. (From Outmans.
Courtest Soc. Petrol. Eng. J. Copyright 1963 by SPE-AIME)

It has been commonly observed that the filtration rate increases as the flow rate increases as
predicted in Equation 6.9. The means of obtaining the shear rate and the fluid loss rate varies
from experiment to experiment. In some studies, the fluid is pumped in an annulus and in others,
the shear is generated by a mechanical wiping action. Annular velocities vary and in some tests
the flow is turbulent.
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Most studies have shown that there is a general correlation between static and dynamic fluid loss.
However, there have been cases where a decrease in the dynamic rate occurred when annular
velocity increased. Increases in the dynamic rate have been observed where concentrations of
fluid loss additives including polyacrylate, CMC and starch have been increased. (This effect is
less noticeable when a static cake has been deposited first.) Studies have also indicated that
although the addition of diesel oil to water-based fluids reduces the API fluid loss value, the
downhole dynamic fluid loss usually increases substantially.

One study by Kueger using a bentonite-based fluid with different additives showed that there was
a considerable difference between the performance of the additives. For example a dispersed
lignosulfonate fluid with an API fluid loss of 11.0 cm
3
had the same dynamic fluid loss as a starch
fluid with an API fluid loss of 4.0 cm
3
. At the same static fluid loss value, the three fluids had
differential dynamic rates that ranged from 0.7 cm
3
/hr for starch, 1.0 cm
3
/hr for CMC and 1.8
cm
3
/hr for polyacrylate. Other work has shown that some polymer-based fluids had much lower
dynamic fluid losses than bentonite fluids. This was associated with the effect of the viscosity of
the liquid phase in polymer fluids.

The effects of high temperatures on dynamic filtration are considered to be comparable to those
observed with static filtration. Mass balance (water consumption) studies have indicated that real
dynamic fluid loss rates are usually lower that those predicted from Equation 6.9. In reality,
experience dictates which HTHP or API fluid loss values are required to successfully penetrate
specific formations in certain areas.

The units used to report the dynamic fluid loss have not been standardized and comparisons
between reported values are difficult. A standard flow rate and differential pressure have not
been defined. The dynamic fluid loss rate should be expressed as cm
3
/45 cm
2
/30 minutes so that
comparisons can be made with the static API test.


6.2.3 Filtration beneath the Bit.

Because of the abrasive action of the bit teeth and the erosive effect of the jets, very little filter
cake forms on the bottom of the hole. Filtration beneath the bit is restricted to an internal mud
cake that forms in the pores of the rock just ahead of the bit.
2
Equation 8.10 has been used to
predict filtration rates at the bottom of the hole while drilling.

Equation 8.10, Bottom hole filtration:

q =
pD
2

4

n RPM
C


Where: q = filtration rate (cm
3
/s)
n = number of cones
RPM = bit revolutions/minute
C = a constant incorporating permeability, pressure and viscosity

Studies which have examined filtration rates beneath the bit show no apparent correlation to API
or HTHP filtration rates.

A theory, the chip hold-down pressure (CHDP) relates the differential pressure between the
fluid column and the formation pore pressure to the bit's penetration rate. As the theory relates to
dynamic conditions, the filtration characteristics of the drilling fluid may apply. This theory
postulates that when a bit tooth penetrates, and a chip is removed, the void space must be filled
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with fluid. If the fluid enters the space the "instant" the rock is fractured the chip is easily
removed. If a longer time is taken to fill the fracture, the chip becomes subjected to the full weight
of the fluid column - becoming more difficult to remove. The fluid's spurt loss may be the most
important filtration characteristic when dynamic CDHP is considered.


6.4 FLUID LOSS CONTROL IN WATER-BASED FLUIDS

6.4.1 Bridging Solids

In order to prevent the loss of whole fluid, a filter cake must be formed on a porous formation.
Solids help to bridge the pore throats. It been shown that the smallest particle that can block a
pore throat has a diameter one third the pore throat opening, as shown in figure 6.3.



Figure 6.3 Minimum size of particles to block a pore


Whole drilling fluid may be lost to the formation before a sufficiently large number of particles
have lodged on the pore throats. This loss is the spurt loss. The required diameter of the
bridging solids can be obtained from the relationship between the diameter of the pores and the
permeability. In conventional sandstone formations, the pore throat diameter in microns
approximates the square root of the permeability measured in millidarcies. Thus, a 100 millidarcy
sand will have a pore throat diameter of about 10 microns. This throat will be bridged by a three
micron diameter particle. For most formations the solids present in barite and clay are able to
form the bridge.

When designing non-damaging, work-over and completion fluids the pore throat size is usually
known. When determining the required bridging material and its size, it is important to consider
the particle size distribution curve. For a given particle size, a wide curve could be more effective
- even at a lower concentration, than a narrow curve (see figure 6.4).

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Figure 6.5 Particle size distribution curve

Loses in more permeable formations such as coarse sands, fractures and vuggy formations may
require the addition of lost circulation material. A large variety of materials have been used to
prevent or cure lost circulation.


6.4.2 Cake Forming Solids

The concentration of solids, their size distribution, shape, and the association between the
particles are all important factors which affect the permeability of the filter cake. The ideal size
arrangement would be a log normal distribution from the bridging size down to sub-micron sizes.
Each size range creates a new pore system which in turn needs to be blocked by finer solids.
This continues down to the sub-micron size range. This effect is achieved in a weighted fluid
treated with bentonite, but may be deficient in low density fluids that containing only drilled solids.

Equation 6.2 can be rewritten to relate the fluid loss to the volume fraction of solids in the filter
cake, C
c
, and the volume fraction of solids in fluid C
m
:

Equation 6.11 Fluid loss vs cake solids

qw = (C
c
/ C
m
- 1)
1/2

This equation states that there should be a linear relationship between the fluid loss volume, q
w
,
and the factor (C
c
/ C
m
- 1)
1/2
. Figure 6.5 depicts a practical view of both the particle size
distribution and the extent of filtrate invasion in a porous formation.


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Figure 6.5 Particle size distribution in a filter cake


6.4.3 Product Selection

When considering fluid loss reducing additives in water-based fluids, it is important to understand
that there are no set laws governing their selection. A drilling fluid program may require a
combination of two additives on one interval, and a completely different additive on the next. A
sea water / polysaccharide fluid may exhibit an acceptable inherent fluid loss, requiring no
augmentation from other products. A flocculated KCl / polyacrylamide fluid may derive its fluid
loss characteristics from several additives. Once the required API or HTHP fluid loss value has
been determined the selection of the proper additive must include the following consideration:

1. Will it tolerate higher electrolytic conditions? Some polymers, including CMC
and polyacrylate don't exhibit good fluid loss reducing qualities in the presence of
high concentrations of soluble salts.

2. Will it tolerate the expected static bottom hole temperature? Most organic
polymers begin to degrade when they are exposed to temperatures above
100C.

3. Can it be used in a weighted system? High solids concentrations may limit the
availability of free water in a system and / or effect rheological properties. Fluid
loss control additives requiring comparably higher concentrations, such as starch
may not be feasible. On the other hand, polyacrylates and lignosulfonates may
effectively reduce the fluid loss and control rheology.

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4. Does it require a preservative? When a fluid loss additive has the potential to
bacterially degrade it becomes necessary to add a biocide. Biocides must be
environmentally acceptable, and maintained at specified concentrations.

5. Will it aid in minimizing formation damage? Producing formations may be
invaded by filtrate containing unsolublilzed polymers. Those polymers having an
acetal linkage in their repeating unit may be broken more efficiently at a later
stage.

6. Is it the most cost effective product? If more than one additive meets the
above criteria, then availability and economics dictate the selection. There are
several situations where the addition of two or more products compliment each
other providing a net cost reduction.

In order to reduce the permeability of the filter cake, there must be some colloidal particles
present. Bentonite forms an effective particle, with many of the particles being less than 0.05
microns. Their thin plate-like shape allows them to act like tiles on a roof. The associations
between the platelets can, however be substantially altered as the chemical environment is
changed.

As the salinity increases, the effectiveness of bentonite as a fluid loss additive decreases and
other colloidal solids must be added. An effective product in salt water conditions, up to
saturation, is pre-gelatinized starch. Starch releases many water swollen sub-micron sized
particles into suspension. Derivatives of lignin, such as sulfonated resins, form colloidal
particles in solution and reduce the permeability of a filter cake. Polymers adsorbed onto clay
particles can act as fluid loss additives, particularly under extreme conditions of temperature and
high salinity.

Equations for both static and dynamic fluid loss show an inverse relationship between the fluid
loss and the viscosity of the filtrate. An additive that increases the viscosity of the filtrate usually
lowers the filtration rate. In practice this situation may be synergistic because the pores in a well
developed filter cake may approach the actual size of the hydrated "water soluble" polymer. Thus
the polymers are concentrated at the pore throat contributing to the bridging effect. This applies
to polymers such as high viscosity carboxymethylcellulose (CMC), high viscosity
hydroxyethylcellulose (HEC) and xanthan gums.

Another synergitic mechanism can be illustrated from the fluid loss characteristics of calcium
carbonate and HEC both alone and together as detailed in Table 6.3. Neither the polymer or the
calcium carbonate provide any fluid loss control, but together the calcium carbonate provides a
fine enough support for the polymer to more effectively prevent the flow through the filter cake.

Table 6.3 Properties of Calcium Carbonate and HEC Solutions

Formulation PV Properties
YP, Pa
Fluid loss
1 kg/m
3
HEC in salt water 20 22 91.5
9 kg/m
3
CaCO
3
in salt water 1 0 No control
1 kg/m
3
HEC + 9 kg/m
3
CaCO
3
17 9 8.2

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Table 6.4 lists some applications of some common water soluble fluid loss reducers. This table
does not constitute a complete picture since some of the products mentioned may be altered
chemically to extend the range of their performance abilities.

Table 6.4 General table relating polymer selection to cost-effectiveness in water-based
systems.


Starch
CMC
hi-vis
CMC
lo-vis
PAC
hi-vis
PAC
lo-vis
Lignite
family

Polyacrylate
Fresh water ok good good ok ok good x
Sea water good x x good good good good
High calcium ok x x ok good good x
High temperature x x x x x ok good
High solids x x ok x good good good
Bacteria x good good good good good good
Producing formations good ok good ok good x x

Prior to drilling, if questions pertaining to product selection remain, laboratory testing may be
necessary to determine the most effective additives. This usually involves testing the
performance of proposed additives under various influences including time, temperature and
pressure.

During the course of drilling, situations may arise which demand an on-sight re-evaluation of
product use. These situations include high concentrations of colloidal solids, electrolytes,
increased temperatures etc. It is always necessary to first pilot test the effects of each change in
even product or concentration implemented. Some polymers develop viscosity in the presence of
salt, while others become ineffective at high concentrations and others fail to perform in the
presence of certain ions.


6.5 FLUID LOSS CONTROL IN OIL-BASED FLUIDS

6.5.1 Cake Formation

Most aspects of fluid loss control in oil-based fluids are comparable to those in water-based
fluids. However, there are some important differences which generate quite different fluid loss
properties and give oil-based fluids important advantages.

Solids must be present to form the bridge and pack together to form a cake as in water-based
fluids. These are typically composed of weighting agents, clays, asphalt derivitives and drilled
solids. These solids are made oil wet by the presence of the surfactants. (They repel water and
attract oil.)


6.5.2 Colloidal Solids

The emulsified water droplets in oil-based fluids effectively act as deformable particles. Having
diameters less than one micron, they form excellent plugging agents. They are surrounded by
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surfactant molecules and are repelled from oil wetted surfaces through interference of the
hydrocarbon chains. Evidence of this mechanism comes from observations. These include the
fact that the fluid loss decreases as the water content increases, and the addition of oil wetting
surfactants help to prevent water from coming through with the oil in the filtrate. Conversely, if a
high fluid loss is required, then the level of surfactants is reduced.

Apart from emulsified water, other colloidal particles are present. The amine treated clay added
for viscosity also provides particles that act as filter cake plugging agents. Amine treated lignite
derivatives and finely ground asphalts may also be added to increase the level of oil-wetted
colloidal sized particles.


6.5.3 Formulation for High Fluid Loss

In some situations, the naturally low fluid loss characteristics of oil-based fluids has led to
particularly low penetration rates when compared to drilling with equivalent density water-based
fluids. (This problem has been reduced to a degree by the introduction of polycrystalline diamond
bits.) It was found, particularly when drilling hard rock, that oil-based fluids having a high fluid
loss improved the penetration rate.

The API filtration rate of an oil-based fluid can be adjusted so that it is zero. A measurable filtrate
volume can only be obtained with higher temperatures, where the viscosity of the oil is lower, and
higher pressures, such as 500 psi rather than 100 psi. If the colloidal solids are left out of the
formulation and lower levels of emulsifiers or different emulsifiers are used, the fluid loss can be
increased up to 30 cm
3
in the API test. The lower state of oil-wetting of the filter cake solids
allows more oil and water to penetrate the filter cake.

6.5.4 Comparison of Static and Dynamic Filtration Rates.

Recent studies examining the relationship between the static and dynamic fluid loss in oil-based
fluids have found an initial dynamic fluid loss that was of the same order of magnitude as the
static fluid loss. When measured in the same units of cm
3
/30 min/45 cm
3
, both were in the range
of 2 - 10 cm
3
with a differential pressure of 500 psi and a temperature of 120C.


6.6 RELATIONSHIP TO HOLE PROBLEMS

6.6.1 Differential Sticking

Differential sticking occurs when the drill collars or bottom hole assembly, lie against a portion of
the hole when the pipe is stationary. The fluid in the filter cake is forced into the formation
increasing the contact area between the pipe and the filter cake. There is potential pressure (p
m
-
p
f
) acting to force the pipe against the wall. This is the difference in the pressure exerted by the
fluid column (p
m
) and the pore pressure (p
f
) in the formation. This pressure is increased at higher
hole angles. The force require to pull the pipe free is given by the following equation:

Equation 6.11:

F = A (p
m
- p
f
) U

where: F = the force
A = the contact area
U = the coefficient of friction between the collars and the cake.
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In practice the pressure is not as high as that given in the equation because the pore pressure
close to the wellbore is higher than the formation pressure. Also, the pores have usually been
damaged by the filter cake. Reduction in the contact area can be made by use of fluted or
spiralled drill collars and stabilizers. The fluid density should also be kept to a minimum value
consistent with well control requirements.

Differential sticking usually occurs in porous sand formations. Hence, it is important for drilling
fluid engineers to be aware of filtration and, especially, cake characteristics when drilling
through sand formations. On-sight evaluations often lead to adjustments to these characteristics,
thereby avoiding the problem. The coefficient of friction of the filter cake can be reduced if the
filter cake is thin and the lubricating properties are well developed through the addition of
lubricants.

Oil-based fluids exhibit properties which minimize the chances of becoming differentially stuck.
The fluid loss values can be low, filter cakes are thin and the high concentration of surfactants
and water droplets in the filter cake make its coefficient of friction very low.

In water-based fluids, differentially stuck pipe is usually freed by spotting oil. The oil will not
enter the pore system of a water-based fluid, so the pressure exerted by the fluid column can
compress the filter cake and reduce the contact area. The oil should be weighted to the same
density as the drilling fluid to keep it from migrating. The effectiveness of the oil may be
enhanced with the addition of specialized surface active compounds.


6.6.2 Formation Damage

Formation damage and the design of drilling and completion fluids for production zones is
discussed in detail in its own chapter. The two main concepts are firstly, that the volume of the
filtrate should be minimal so that the depth of invasion will not be small and secondly, that the
filtrate which does invade the production zone should not alter the permeability of the formation.

While drilling in the production zone, there should be an adequate concentration of bridging
solids of appropriate size. Porous formations can then be quickly sealed off and whole fluid
invasion can be limited. This is important because colloidal sized particles in the fluid can cause
formation damage. Solids that are added are sometimes chosen so that they can be removed at
some later stage. Sized salt crystals are added to brine systems as these can be removed by
fresh water washes. Calcium carbonate may be added as it can be removed with an
hydrochloric acid wash. Resins may be added if an oil soluble bridge is desired. It is important
to add solids so that a competent filter cake can be formed. A proper cake will help to clean the
invading filtrate of damaging colloidal sized solids and polymers.

Consideration should also be given to the possible reaction between the filtrate and the formation
fluids and solids. For example, the pore fluids of some formations contain concentrations of
soluble barium. This can be precipitated to form a damaging scale of barium sulfate, if the drilling
or completion fluid contains sulfate ions. Some formations contain significant quantities of clay
minerals in the pore throats. An alkaline or fresh water filtrate can disperse these clays, causing
them to block the pore throats. Several other examples of relations between filtrate and formation
fluids are discussed in Chapter 15, Production Zone Drilling. Low fluid loss and a thin filter cake
will also minimise these effects.
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6.6.3 Borehole Stability

The topic of Borehole Stability is considered in Chapter 10, where the influence of system design
on the stability of the formation is discussed. A key to maintaining borehole stability is that the
rocks are partially supported by the pressure exerted by the fluid. Further, the fluid or filtrate
should not react with the rocks. Theoretically, these objectives will be met if a dense enough
fluid could lay down an impervious coating on the hole wall as the hole is drilled.

It has been found that control of fluid loss in formations such as shales (where permeability of the
rocks is less than of the natural filter cake) can add to the stability of the formation. Also,
movement of the formation into the hole creates a zone where the permeability is higher due to
the formation of micro-fractures. If these fractures can be sealed then the partially failed rock can
be supported by the fluid's weight. Inhibitive polymeric muds such as the partially hydrolyzed
polyacrylamide (PHPA) will act in this manner. Additives such as gilsonite and sulfonated resins
will also act to seal the fractures, particularly in the more brittle formations.
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References

1 Darley & Grey, Composition and Properties, 298.
2 Darley & Grey, Composition and Properties, 310.


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CHAPTER 7

WATER-BASED FLUIDS

7.1 KEY POINTS AND SUMMARY

7.2 HISTORY OF WATER-BASED FLUIDS

7.3 DRILLING FLUID SELECTION
7.3.1 Categorizing Water-Based Fluids
7.3.2 Selecting a Drilling Fluid
7.3.3 Planning a Drilling Fluid Program

7.4 COMPONENTS OF WATER-BASED FLUIDS
7.4.1 Make-Up Water
7.4.2 Weighing Agents
7.4.3 Viscosifiers and PHB
7.4.4 Filtration Control Additives
7.4.5 Rheology Control Additives
7.4.6 Shale Stabilization Additives
7.4.7 Lost Circulation Materials
7.4.8 Conditioning Chemicals
7.4.9 Inorganic

7.5 WATER-BASED SYSTEMS
7.5.1 Mixing, Converting and Displacing
7.5.2 Spud Mud
7.5.3 Low-Density Fluids
7.5.4 Clear Water Systems
7.5.5 Gel-Based Systems
7.5.6 Salt Saturated Systems
7.5.7 Calcium Systems
7.5.8 KCl Systems
7.5.9 Aluminum Sulfate Systems
7.5.10 PHPA Systems

7.6 Ava Drilling fluids Systems
7.6.1 Spud Muds
7.6.2 Water Drilling
7.6.3 Bentonite / Chemical Muds
7.6.4 Dispersed Muds
7.6.5 Inhibitive Drilling Fluid Systems


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7.1 KEY POINTS AND SUMMARY

Today, so many different types of water-based systems are in use that it is difficult to list or even
categorize them all. This chapter attempts to offer ideas and assistance to those with the task of
selecting a drilling fluid and planning a drilling fluid program.

Various components of drilling fluids are included and described, as a quick reference for those
experienced in drilling fluid engineering or as an aid for those beginning their careers. The final
part of the chapter describes some of the systems currently being used by Ava Drilling Fluids. A
brief history of the generic fluid is followed by a description of how to mix and maintain some of
Ava's specific systems.


7.2 HISTORY OF WATER-BASED FLUIDS

The use of water to aid in the removal of the cuttings generated by percussion drilling dates back
to 1,000 B.C. in China. The use of water as a cuttings removal medium for rotary drilling was
patented in the United States by Robert Beart in 1844. In 1887 M.J. Chapman patented a clay
containing mixture for its "plastering properties". The wall-building characteristics of clays soon
became recognized throughout the U.S. and by 1913 the higher density of clay fluids was seen
as means of pressure control.

In 1922 Barite was used to increase the specific gravity of drilling muds. U.S. patent was issued
for the addition of heavy minerals to drilling mud in 1926. This ushered in the primary age of
drilling fluids technology. During the 1920's, specific products were developed to treat or improve
certain properties of drilling fluids. In 1928, Bentonite as an additive for overcoming hole problems
gained widespread use. By 1929 a specific blend of Barite and Bentonite was made available
and in 1930 the first proprietary thinning agent was introduced.

The next three decades saw a remarkable increase in drilling fluids research and development.
This came about as the industry saw that improvements in drilling fluids technology benefited
both drilling and production economics. This was a time when a variety of drilling fluid systems
were developed, some of which are still in use today. Because these systems used a wide range
of components, and retained different properties, the development of testing procedures and
techniques also began at this time. During this period the majority of the technological
advancement in drilling fluids occurred in the United States.

The use of dissolved salt for control of borehole stability was patented in 1931. Salt systems were
developed and used extensively in the 1930's. The use of salt systems promoted using pre-
hydrated Bentonite, Attipulgite clay and Gelatinized Starch. In the late 1930's high pH fluids were
used because of their superior flow characteristics and tolerance for drilled solids. High pH fluids
were the predecessor of the "lime muds" used in the 1940's and early 50's.

The 1950's saw the development and advancement of oil emulsion fluids, low solids fluids
viscosified with CMC, and gypsum treated fluids. Gyp fluids were developed in Western Canada
as a means of drilling anhydrite formations. This marked an end to the absolute U.S. domination
of the advancement of drilling fluids technology.

The 1960's and seventies saw the industry turn its attention toward the development of synthetic
polymers, inhibitive fluid systems and invert emulsion systems, discussed in Chapter 8. Polymer-
extended gel systems were introduced in 1960. Also in that year, the use of Potassium as an
inhibitor was successfully applied in Venezuela. In 1967 KCl / Gel / XC Polymer fluid was used to
drill permafrost in Northern Canada. Shell Polymer Mud (SPM) was being developed for use in
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the 1970's in Western Canada. This was the first KCl / PHPA fluid. PHPA systems became
common in many other areas during the 1970's.

In the 1980's increased attention was directed toward environmental concerns. New low-toxicity
products and systems were developed, including low-tox oil-based fluids and phosphate fluids.
The issue of hot holes was also addressed, resulting in the development of exceptionally tolerant
products and systems. This Manual addresses both, low-tox oil-based systems, and high
temperature water-based systems. The age of horizontal drilling required better lubricants with
modified rheological properties. These requirements were often combined with a non-damaging
fluid system application. Table 7.1 classifies various drilling fluid systems by the decade in which
they gained acceptance and became widely used in our industry.

The 1990's and beyond hold increasing challenges for the advancement of drilling fluids
technology.


TABLE 7.1 THE EVOLUTION OF
DRILLING FLUID SYSTEMS

1890 - 1920

Water / Clay

1920's

Water / Barite / Bentonite

1930's

Salt Systems

1940's

Lime Systems

1950's

GYP Systems
Oil Emulsions

1960's


Low Solids Systems
Invert Emulsions

1970's

KCl / PHPA Systems

1980's

High Temperature Formulations
Lo-Toxicity Invert Emulsions


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7.3 DRILLING FLUID SELECTION

7.3.1 Categorizing Water-Based Fluids

Throughout the short history of oil well drilling fluids, various authorities and suppliers have
classified fluids systems into various broad categories. This exercise becomes increasingly
difficult as the selection of various systems becomes more diverse. Table 7.2 shows how three
separate authorities have recently classified water-based fluids.


TABLE 7.2 CLASSIFYING WATER BASED FLUIDS


Composition & Properties
of Drilling & Completion
Fluids*


World Oil (After
API and IADC)

United States Environmental
Protection Agency Approved
Generic Fluids Systems


Air / Mist / Foam

Air / Mist / Foam

Seawater / Potassium / Polymer

Water Dispersed Seawater/Lignosulfonate

Spud Mud Non-Dispersed Lime Mud

Salt Water Systems Calcium Treated Non-Dispersed Mud

Lime Systems Polymer Systems Spud Mud

Gyp Systems Low Solids Seawater / Freshwater Gel Mud

CL-CLS Systems Saturated Salt Lightly Treated Lignosulfonate
Freshwater / Seawater Mud

Potassium Systems Workover Lignosulfonate Freshwater Mud

Oil-Based Fluids Oil-Based Fluids


* Gulf Publishing Company, Houston, Texas


Others classify water-based systems more broadly. These include:

1. Salt Water / Fresh Water
2. Dispersed / Non-Dispersed
3. Inhibitive / Non-Inhibitive
4. Clay Fluids / Polymer Fluids

A problem exists in that sometimes the systems or functions fall into more than one category. For
example, when a fresh-water system is densified to stop overpressured shales from spalling, it
also becomes a type of inhibitive system.

Most drilling fluids systems today are flexible. That is, all water-based systems can be dispersed,
most Bentonite systems contain some polymer - even if its the peptizing agent, and most
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polymer systems contain at least some (formation) clay. A PHPA system is an inhibitive system
and a polymer system, in salt or fresh water, but PHPA may also be a component of a Gel and a
potassium system.

Today, drilling fluid systems are often generically classified by their density, base fluid, and
principal ingredient, for example:

1. Unweighted Gyp - PAC
2. Fresh water - Gel
3. Weighted - Seawater - Polymer

The drilling fluid systems described later in this chapter are included because they are frequently
used by Ava.


7.3.2 Selecting a Drilling Fluid

As oil wells become more difficult to drill, the problem of selecting the best drilling fluid can
become fairly complex. Today, there are so many fluid systems available that the analysis is
sometimes computer assisted.

There are no approved criteria for drilling fluid selection. Different operators have their own
policies and processes. Often one operator will identify and successfully use a drilling fluid
system adjacent to another operator using a different system, just as successfully. The worst
case occurs when a fluid system must be replaced, or when a drilling operation fails because an
inappropriate fluid system was chosen.

Contingency planning should be a part of all drilling fluids programs. Time spent mixing,
circulating or conditioning drilling fluids due to an oversight in the planning phase can be
expensive. Mixing, displacement and spotting procedures should be carefully planned in advance
to avoid lost time.

The most efficient selection of casing setting depths is often influenced by the ability to drill and
case formations with the same density and type of fluid. Often an interval has an engineering-
oriented or geology-oriented objective. A good drilling fluid will aid in meeting these objectives
and often enhance them. Engineering parameters are extended if interval lengths can be
increased, and if geological evaluation can be improved with proper fluid formulation. Thus, if the
selection of a drilling fluid system seems complicated, it is often advantageous to initially consider
each interval separately. Then a step-by-step process can be implemented in the search for the
best fluid system.

Ava suggests using the following steps. (Other operators and service companies use variations
of this):

1. Define the objective of the interval.
2. Identify factors, which may prevent rapid and economical realization of the
objective.
3. Select a drilling fluid system(s) with respect to all of the demand criteria of the
interval. (Obviously, it would be best if one system could be used throughout the
well).

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The first step, defining the objective of an interval is usually the easiest. Most intervals have
engineering objectives. Various intervals are commonly called:

1. Top Hole
2. Intermediate Hole
3. Main Hole or Slim Hole

Top hole or surface hole, may actually be up to three intervals. Offshore Arctic wells usually drill
glory hole, conductor hole and surface hole. The engineering priority for top holes is to cement a
string of casing (pipe) in place such that while drilling successive intervals, excessive sub-surface
pressures must be directed up through it. Drilling fluid systems used to drill top hole are often
called Spud Muds.

Intermediate hole may consist of one or more intervals. The objective is to drill to the producing
formation as quickly as possible. Geological evaluation is usually conducted as drilling proceeds.
Sometimes engineering tasks such as kicking-off or steering are also performed on intermediate
hole. Pressures and borehole stability often dictate the length of an intermediate interval.
Sometimes an intermediate interval uses two types of drilling fluid systems such as in the Rocky
Mountain region where air or clear water is used prior to "mud up". Often it isn't necessary to set
intermediate casing - main hole is drilled from under the surface casing shoe.

The main hole or slim hole is the interval that penetrates the producing formation. The objective
is geological. The goal of an exploration well is to evaluate the production potential of a formation.
With production wells, the objective is to penetrate the zone without damaging its ability to allow
fluids to flow into the wellbore. (A good exploration well often ends up being a production well).
Often engineering objectives must also be met on main hole. An example is a well drilled
horizontally through a producing zone.

The second step in drilling fluid selection involves identifying the factors, which might prevent
the objective of the interval from being met in a timely and economical manner. It is the function
or functions of the drilling fluid system to overcome these limiting factors. (See Chapter 1 for a
review of the functions of drilling fluids). Some areas of concern are listed below:

1) Environmental & Safety Considerations
2) Abnormal Formation Pressures
3) High Temperatures
4) Excessive Deviation
5) Borehole Instability
6) Production Zone Damage
7) Others

Usually formation damage or high temperatures are not a problem on top hole. However, it is
possible for the other limiting factors to occur on any interval.

A primary objective of any drilling fluid research is to instill environmental and safety
considerations into system and product development. The same concerns apply when choosing
a fluid system to drill with. In some locations, certain fluid systems are not environmentally
acceptable. These might include - but are not limited to - salt systems, high pH systems or
chrome containing systems.

High temperatures, overpressures and excessive deviation are all conditions or problems,
which can be minimized or alleviated with proper drilling fluid design. Usually the components and
properties of water-based fluids begin to become adversely affected at temperatures above
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100C. Water - based systems specially formulated to perform at high temperatures are
discussed in a separate chapter of this Manual. Abnormal formation pressures rule out the use of
low density, low cost fluids. On high angle wells, fluid formulation may have to be modified in
order to enhance cuttings cleaning characteristics. Low shear rate viscosities, flow regimes and
lubricity characteristics may be the most important fluid properties on these wells. The
competency of the formation usually dictates the flow regime and thus the fluid system and
properties. The problem of cleaning in inclined holes is discussed in the chapter on Rheology,
Cleaning and Pressure Losses.

Borehole stability problems can occur on any interval. The term borehole instability usually
refers to holes becoming either bigger or smaller due to one of a number of possible causes.
Some examples are listed below:

1) Gravel and Fractured Formations
2) Evaporate Formations
3) Tectonic Squeezing
4) Overpressured Shale
5) Zones Containing Gas Hydrates
6) Permafrost
7) High Formation Dip
8) Water Sensitive Formations

The last example, water sensitive formation presents one of the most intricate issues when
attempting to identify the potential problems in an interval. In a new field, it is important to obtain
and analyze as much data as possible from various formations, so that future drilling fluid
systems can be changed or modified appropriately. Prior to drilling offset wells, logs can provide
data on formation dip, geology, temperature and pressure / fracture gradients, and in situ water
content. While drilling, shale samples should be obtained for laboratory testing. A well-preserved
core sample is by far the best source of data. The best swelling inhibition mechanism can often
be predicted if data is analyzed properly. Analytical tests include:

1) X-Ray Diffraction
2) Cation Exchange Capacity
3) Balancing Salinity
4) Swelling Measurements
5) Dispersion Tests
6) Various Types of Stress Tests

Samples may be tested in different fluids using different inhibition mechanisms, various
concentrations of chemicals or even a combination of 2 mechanisms. (In a KCl / Polymer system
the encapsulating polymer uses a physical mechanism while the potassium ion uses a chemical
inhibiting mechanism). Often a reduction in cake permeability and fluid loss is all that is required
to control problems resulting from water sensitive clays. Selection of the proper fluid loss additive
is discussed in Chapter 5 and Chapter 6. The chapter on Borehole Stability (10) makes it clear
that hole instability is a complex problem, especially when the relationship between drilling fluid
chemistry and borehole stability is addressed.

The objective of main or sum hole is usually to penetrate the zone of interest for evaluation or
exploitation purposes. Proper evaluation or full production may be affected if the wellbore fluid
causes production zone damage. The chapter on Production Zone drilling, (14) expands on the
following damage mechanisms and how they can be avoided:
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1) Water Block
2) Emulsion Block
3) Oil Damage to Gas Reservoirs
4) Particle Invasion
5) Precipitant Formation

Other common problems, which may impede achievement of the objective on any interval,
include:

1) Severe Loss Zones
2) Water Flows
3) H
2
S (also a safety consideration)
4) Bacteria
5) Differential Sticking
6 The Formation of Hydrates (safety also)
7) Special Logging Requirements

The third step, deciding on a system, is a matter of assessing the available options, keeping in
mind the demand criteria of each interval and any environmental regulations. Shale analysis often
points towards one obvious choice - such as oil-based fluid. When several alternatives exist,
different factors can help narrow the choice down. The most obvious is to attempt to choose a
fluid, which can be used on most or all of the intervals. Other eliminating factors are listed below:

1. Safety
- Personnel
- Environment
- Equipment

2. Logistics
- Remoteness of Location & Transportation
- Season - Weather Conditions
- Using the Least Number of Fluid Systems per Well
- Complimentary Equipment Requirements
- Testing & Lab Equipment
- Bulk-Handling Equipment
- Mixing Equipment
- Solids Control Equipment
- Storage Facilities
- Cuttings Treatment Equipment
- Filtration Equipment

3. Economics
- Availability of Base Fluid & Chemicals
- Maintenance Costs
- Buy-back Possibilities
- Disposal Problems

4. Bit Hydraulics and ROP Optimization

5. Past Experiences
- Often aids in Selection, by a Process of Elimination

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7.3.3 Planning a Drilling Fluids Program

Formulating a drilling fluids program is usually carried out in conjunction with the Operator's
geology and engineering departments. Some Operators choose to formulate their own drilling
fluids programs. Often they request one from a service company - sometimes as part of a bid
package. The drilling fluid program should address all possible issues and propose appropriate
contingency plans. It may include:

1. Engineering Parameters
2. A Lithological Description
3. Pore Pressure Prediction
4. Casing Setting Depths
5. A Well Profile with KOP and DOP
6. Proposed Fluids System - Usually by Interval
7. Chemical Concentrations
8. Required Fluid Properties
9. Lab Testing Results
10. Offset Well Information
11. Contingency Formulations and Procedures
- LCM Pills
- Barite Plugs
- Viscosity Sweeps
- Lubricity Pills
- Procedures and Directives from Regulatory Agencies
- Corrosion Control Program
12. A Materials and Volume Estimate by Interval
13. A solids Control Program
14. Price List

The properties of the drilling fluid of particular importance are:

1. Density - Formation Pressure Control
2. Rheology - Optimum Cleaning and Hydraulics
3. Salinity or Polymer Content
4. Alkalinity


7.4 COMPONENTS OF WATER-BASED FLUIDS

Classifying the constituent chemicals, which are blended together to make various drilling fluid
systems, is a somewhat arbitrary task. This is because so many different chemicals affect more
than one property or more than one function. An example is the affect that Lignosulfonate has on
both the rheological properties and the fluid loss properties.

In some systems PAC is the primary viscosifier, Gyp-PAC systems are used by some North Sea
Operators. However, in an unweighted KCl/Polymer fluid the addition of even small amounts of
PAC will cause deflocculation and loss of cleaning properties. The water-based fluid components
described in the ensuing text can usually be added to most water-based systems providing the
proper procedures are followed. It is the combination and proportions of these components, which
make up individual fluid systems. This section has been included in this Manual as a quick
reference. For more in-depth descriptions of water-based and other drilling fluid components,
consult the Ava Product Data Book, or call youre nearest Ava Technical Service Department.

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7.4.1 Make-up Water

Water is the most important single substance involved in water based drilling fluids technology.
The functions of water include; provision of the initial viscosity; solvation of salts, suspension of
colloids and transfer of heat. The availability and chemical content of the make-up water must be
considered in the planning stage of any well. Some of the unusual characteristics of water were
discussed in the chapter on Basic Chemistry. They include: high surface tension, high heat of
vaporization, the ability to form hydrogen bonds, the ability to cause dissociation of ionic crystals
such as salts, and bases, and the fact that hydrated ions and particles exhibit modified properties.
Water is essentially incompressible; therefore, increased resistance to flow due to volume
reduction is negligible. The temperature effects on water's properties are also minimal, although
temperature does have pronounced effects on the properties of water-based fluids. Unlike most
other substances, water expands when it freezes under normal pressure.

These characteristics of water affect each step in the drilling operation from spud to completion.
In some locations the availability of fresh water eliminates the choice of certain fluid systems and
dictates complementary equipment such as premix tanks. Often hard water must be treated
chemically or fresh water must be fabricated from seawater before chemicals and products can
be added. Fabricated water is called drill-water on offshore rigs.

Brackish water and seawater contain a wide variety of solvated ions. For this reason it is often
necessary to alter fluid system formulations when commercial products are added to seawater-
based fluids. The obvious step is to designate a premix tank, for prehydrating Bentonite.
However, the performance of many water-soluble polymers is also affected when they are used in
a salty / hard environment. This applies especially to viscosifying and filtrate reducing polymers.
Usually concentrations have to be increased to obtain properties similar to those obtained with
fresh water. Table 7.3 shows the concentrations of some of the ions found in a typical seawater
analysis.

TABLE 7.3 TYPICAL SEAWATER
ANALYSIS

ION

CONCENTRATION (mg/L)

Chloride 19 000
Sulfate 2 700
Bicarbonate 100
Bromide 60
Borate 25
Nitrate 0.7
Phosphate 0.1
Fluoride 1.3
Sodium 11 000
Magnesium 1 300
Calcium 400
Potassium 400
pH 7.5 - 8.5

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7.4.2 Weighting Agents

Drilling fluids are densified or weighted up to perform one of two functions as outlined in chapter
one. That is, to control sub-surface pressures or stabilize incompetent formations. For a material
to be a viable solid phase weighting agent, it must have a high specific gravity, be non-abrasive,
readily available, economical and safe. Table 7.4 lists the solid phase weighting materials
supplied by Ava.

TABLE 7.4 WEIGHTING AGENTS

COMMERCIAL
PRODUCT



MINERAL


PRINCIPLE
COMPONENT


SPECIFIC
GRAVITY


MOH'S
HARDNESS


Calcium
Carbonate

Calcium
Carbonate

CaCO
3


2.65
2.71

3


Ferrowate

Iron
Carbonate


FeCO
3



3.7 - 3.9


3.5 - 4.0


Barite

Barium
Sulfate


BaSO
4



4.2 - 4.5


2.5 - 3.5

Plus-5

Hematite

Fe
2
O
3


4.9 - 5.3

5.5 - 6.5


Barite is by far the most common weighting material. It is easily dispersed, and virtually insoluble
in water. It is almost completely inert in water-based systems and is relatively non-abrasive. Table
7.5 lists the API qualifications for Barite. Note the spec for calcium. Some impure grades of Barite
contain quantities of Calcium Sulfate, which is a contaminant in water-based fluids. Volume II of
this Manual contains equations for densifying with Barite.


TABLE 7.5 BARITE REQUIREMENTS FOR API SPECIFICATION

Specific Gravity: 4.20, minimum


Wet Screen Analysis:

Residue on U.S. Sieve (ASTM) no. 200: 3.0% maximum

Residue on U.S. Sieve (ASTM) no. 325: 5.0% minimum


Soluble Alkaline Earth Metals as Calcium: 250 ppm, maximum



The other products are utilized because they have specific applications. Salts can be used to
increase the density in water-based fluids to a limited density range. Salts can be used as solid
phase weighting materials in saturated systems - see the chapter on Production Zone Fluids. The
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Calcium Carbonate products are used mainly as bridging or weighting materials for both oil and
water-based production zone fluids. They are soluble in HCl.

Galena isn't normally used in drilling fluids because it is expensive and it requires special
handling. However, it is an excellent contingency product where control of a blowout is required.
Slurries up to 3800 kg/m
3
can be prepared with Galena.


7.4.3 Viscosifiers and PHB

Viscosifiers are added to drilling fluids to improve their cleaning and suspension functions.
Primary viscosifiers for water-based fluids are normally clays or polymers. Any primary viscosifier
must interact with the base fluid to some degree. This is accomplished by the shape and / or
surface changes on the particle or molecule. The best viscosifiers impart both psuedoplastic and
thixotropic properties to a fluid. The selection of the most appropriate product is dependant upon
economics, logistics and the expected fluid environment. Other chemicals including salts and
bridging polymers may enhance the properties imparted by the primary viscosifiers. Table 7.6
lists some of the viscosifiers Ava supplies. It can be seen that all of the products are either clays
or polymers.

TABLE 7.6 VISCOSIFIERS

TRADE
NAME


MATERIAL

PRINCIPAL
COMPONENT


APPLICATION

SECONDARY
BENEFIT


Avabex

Polyacrylate

Acrylic Polymer

Bentonite
Extender

Fluid Loss
Reducer

Policell

Polyanionic
Cellulose

Substituted
Cellulose Polymer

Viscosifier - used in
Special Applications
(Gyp / PAC)

Fluid Loss
Reducer

Avagel

Bentonite

Hydrous Aluminum
Silicate

Viscosifier - May
Require Pre-hydration

Fluid Loss
Reducer

Natrosol

Hydroxy Ethyl
Cellulose

Cellulose Derivative

Completion Brine
Viscosifier

Minimal
Damage

Visco XC
84

Xanthan Gum

Bio-Polysaccharide

Viscosifier - All Water
Based Fluids

Fluid Loss
Reducer


Visco XCD

Xanthan Gum

Modifed Bio-
Polysaccaride

LSR Viscosifier

Fluid Loss
Reducer

Avagum

Guar Gum

Natural
Polysaccharide

Viscosity Sweeps in
Large Holes

Drilled Solids
Flocculant



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Bentonite is often used as the primary viscosifier in systems using seawater, produced brine, gyp
or a commercial salt. In these systems Bentonite must be prehydrated in fresh water. The slurry
is referred to as prehydrated Bentonite or PHB.

When prehydrating Bentonite, 110 - 140 kg/m
3
is usually added to fresh water. The clay yield can
be improved if; the water is warm and well agitated, the calcium is removed and the pH adjusted
to about 9. Several hours should be allowed for hydration and dispersion to occur. Often
lignosulfonate is added to PHB to allow for the addition of extra Bentonite and to provide better
stability (duration) in terms of viscosity and filtration characteristics in the saline environment. This
is also a good way of maintaining a slight concentration of lignosulfonate in a flocculated system
such as a KCl/Polymer fluid. Since lignosulfonate has clay encapsulating properties, as much
Bentonite as possible should be added to the PHB mixture prior to adding the lignosulfonate.


7.4.4 Filtration Control Additives

Filtration control additives are blended into water-based fluids to reduce the amount of liquid
phase forced into the formation rock. Up to three different mechanisms are used by these
products:

1. Reduction of cake permeability by deflocculation and compression.
2. Reduction of flow-rate by viscosification of the liquid phase.
3. Pore plugging.

Thus, viscosifiers and deflocculants usually aid in fluid loss reduction. Often fluid loss reducing
agents complement one another in a synergistic manner, similar to that of viscosifiers. Refer to
the chapter on Fluid Loss for a more detailed description of fluid loss mechanisms. Table 7.7 lists
some of the filtration control additives offered by Ava. For a complete list, refer to the Ava Product
Data Book.


TABLE 7.7 FILTRATION CONTROL ADDITIVES

TRADE
NAME

PRINCIPLE
COMPONENT


APPLICATION

SECONDARY
FUNCTIONS

Avalig Natural Coal Product Economical Filtration Control Deflocculation
Avalig C Sodium Humate Filtration Control in High-temp.
Saline Evnironments
Deflocculation
Victosal Modified Starch Filtration Control in Highly Saline
Environments
Acid Soluble
CMC Carboxymethyll Cellulose Economical Filtration Control Some
Viscosification
Policell Polyanionic Cellulose Filtration Control in Brackish
Environments
Moderate
Deflocculation in
Unweighted Salt
Systems
Avapoly HT Synthetic Polymer Filtration Control > 200C Moderate
Deflocculation

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7.4.5 Rheology Control Additives

Rheology control additives are generally used to extend the performance limitations of water-
based fluids. This usually means temperature limitations and solids concentration tolerance.
These products are called deflocculants or thinners. Products which reduce the required
concentration of a primary viscosifier are called extenders or flocculants. Deflocculants (thinners)
reduce most rheological and thixotropic properties by decreasing the degree and strength of the
colloidal particle associations in drilling fluid suspensions. On the other hand, flocculants increase
the degree and strength of these associations. The chapter on Clay Chemistry provides a more
detailed explanation of these mechanisms. Table 7.8 shows some of the deflocculants offered by
Ava.


TABLE 7.8 DEFLOCCULANTS

C0MMERCIAL
NAME

PRINCIPLE
COMPONENT


APPLICATION

SECONDARY
FUNCTIONS


SAPP

Sodium Acid
Pyrophosphate

Powerful Deflocculant. Prevents
Mud Rings

Calcium
Precipitation

Avafluid G71

Ferro Chrome
Lignosulfonate

Deflocculant in all Water-based
Systems

Filtration Control

Avathin

Acrylic Acid

Deflocculant in all water based
Systems

Filtration Control

Polifluid

Sodium Salt
Polycarboxilc Acid

Effective Thinner Up To 250C


Filtration Control


7.4.6 Shale Stabilization Additives

The topic of borehole stability is so far reaching, it has been mentioned in most of the chapters in
this manual. Shale stabilization itself is a broad term lacking definition and method. The preceding
text, "Selecting a drilling fluid" mentioned several methods of determining the best stabilizer for
water-sensitive clays formations. Depending on the specific nature of the shale, any of several
available materials may impart favorable results. Mechanisms, which are recognized as
contributors to borehole stability are:

1. Balanced Activity
2. Cation Exchange
3. Encapsulation
4. Plastering (Plugging Micro fractures)
5 Increased Fluid Density

These mechanisms are discussed in the chapter called Borehole Stability. Table 7.9 shows some
of Ava's encapsulating and plastering products, which contribute to the stabilization of shales.

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TABLE 7.9 SHALE STABILIZATION ADDITIVES

Cation Exchangers:

Potassium Calcium Aluminum

Encapsulators:

(Polyacrylamide)

(Lignosulfonates)

(Most PAC's)

Plastering Materials:

Gilsonite HT (Bituminous)


7.4.7 Lost Circulation Materials

Lost circulation materials (LCM) are used to stop excessive losses of whole drilling fluid to
permeable or fractured formations. Lost circulation materials are classified as flaky, granular or
fibrous. Mechanisms for stopping losses include, matting, bridging and plugging. Many
substances have been recommended for regaining circulation. Table 7.10 shows some of the lost
circulation products supplied by Ava.

Table 7.10 Lost Circulation Materials

FLAKY

FIBROUS

GRANULAR
Kwik Seal OM Seal Sand Seal
Mica Granular
Avacarb


Flaky materials include cellophane, mica and wood chips. They are best for plugging and bridging
porosity and microfissures. Fibrous materials include pulverized sugar cane stalks, cotton fibers
and wood fibers. They work by penetrating and forming a mat on fractures or pores which other
fluid solids can build on. Granular products include diatomaceous earth, ground walnut hulls and
calcium carbonate. They work by plugging pores and microfissures. Many products contain a
mixture or proprietary blend of these. Often, the choice of which product to use is based on trial
and error, experimentation, or previous experience in an area.

Lost circulation materials are often incorporated into various lost circulation plugs and slurries,
including cement slurries, "gunk plugs" etc. In Chapter 16, the problem of lost circulation is
discussed in greater detail.


7.4.8 Conditioning Chemicals

Ava offers a complete array of conditioning chemicals for water-based drilling, completion and
workover fluids, some of which are listed in Table 7.11. A close study of the table indicates that
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many of these products are used to alter fluid chemistry or properties, usually for the purpose of
negating or minimizing various problems encountered while drilling with water-based fluids.

TABLE 7.11 CONDITIONING CHEMICALS
a


Alkalinity
and pH

Surfactant

Lubricant

Corrosion
Inhibitor

Bacteriacide

Foamers/
Defoamers

Spotting
Fluids

Emulsifier


Caustic
Soda
Soda Ash

Avadeter


Ava
Greenlube


Deoxy SS


Avacid 50



Avasil



Avatensio



Avoil PE



Lime
Gypsum

Avasurfo

Avalube

Incorr

Avacid F/25

Avafoam
S1


Deblock S



Avoil SE

Sodium
Bicarbonate

Ecol Lube

Zinc
carbonate



Avoil WA

Potassium
Hydroxide



Avades
100

a
Descriptions of these and other conditioning chemicals are found in the Ava Product Data Book


pH and alkalinity control many drilling fluid system properties. The solubility and effectiveness of
most water-based drilling fluid components are improved at proper pH conditions, including
drilling fluid clays, polymers and thinning chemicals. Alkalinity is important in terms of suppressing
the solubility of contaminating ions and molecules such as Ca
2+
, Mg
2+
, H
2
S and CO
2
.

Surfactants are used to alter the surface chemistry of drilling fluid components, steel pipe, or
formation material. They modify or reduce surface tension at the interface of various water-based
fluid phases. Surfactants are used to combat bit balling and cuttings sticking to drilling tools. This
results in better ROP's and easier wiper trips. Surfactants are discussed in detail in the Polymer
Chapter (5).

Lubricants are used to reduce rotary torque and hole drag in deep, directional holes. Today
holes are being drilled with both a kick-off point and a drop-off point. That is, they are "S" shaped.
Ava has been involved in planning and servicing several such wells which built to 60, then
dropped to 30, with a horizontal displacement of almost 3,000 m - with water-based fluids. The
selection and compatibility of both solid phase and liquid phase lubricants is tested using fairly
elaborate equipment. Before using solid phase lubricants, remember to double-check on their
compatibility with mud motors, telemetry equipment and coring equipment, at the proposed
concentrations.

Corrosion inhibitors are a broad class of conditioning chemicals. They are expected to work in
corrosive environments by various mechanisms or combinations of mechanisms. Corrosive
gasses include H
2
S, CO
2
and 0
2
, or any combination of all three. Several factors affect corrosion
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rates, including temperature and pressure. Table 7.11 lists 13 different corrosion inhibitors
supplied by Ava. For a more in-depth discussion, turn to the chapter on Corrosion (16).

Bactericide is the generic name given to any substance that kills bacteria. Bactericides vary
greatly in their potency and specificity. They may include other organisms, chemical compounds
or even short-wave radiation. Bacterial growth may result in the destruction of drilling fluid
polymers - resulting in a loss of filtration or suspension properties. Sulfate Reducing Bacteria
(SRB) can generate H
2
S gas in concentrations high enough to be lethal. Microorganisms produce
enzymes, which also attack and decompose organic materials. The enzymes however can't be
treated out or destroyed. Thus the selection of the proper bactericide is extremely important.

Foam in drilling fluids is undesirable because slush pump and solids equipment efficiency rates
are hampered by it. Foam also increases corrosion rates and leads to erroneous PVT estimates.
When not treated properly, severe foaming problems can lead to a complete inability to pump.
Defoamers are used to reduce the tendency of brackish or salt-water fluids to foam. Defoamers
are also used to remove entrained air or gas from fresh water fluids. They work by reducing the
surface tension of bubbles. Because so many variables can contribute to foaming problems, pilot
testing is often conducted at the rig to aid in choosing the most efficient product.

Spotting fluids are used to aid in freeing differentially stuck drill pipe. They often contain a blend
of several constituents. The main working mechanism involves drying or dehydrating the filter
cake.

Oil is occasionally added to water-based fluids to improve certain properties. Up to 10% and more
oil may become entrained in a water-based fluid after an oil-bearing formation has been drilled. If
the water and oil phase are immiscible, in the mud pits, an emulsifier must be added. Often, a
lignosulfonate product suffices adequately.


7.4.9 Inorganics

Inorganic chemicals perform a diverse number of functions in water-based fluids, including,
densification contaminant precipitation, corrosion control, pore plugging and alkalinity control.
Mixtures of these compounds can be blended to assimilate the composition of evaporate
intervals. Table 7.12 lists a brief description of some of the inorganic chemicals supplied by Ava.

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TABLE 7.12 INORGANIC COMPOUNDS
a


NAME

ABBREVIATION

DESCRIPTION

USES


Ammonium Bisulfite

NH
4
HSO
3


White Crystals

Oxygen Scavenger

Calcium Bromide

CaBr
2


White Powder

Heavy Clear Brines

Calcium Chloride

CaCl
2


White Granules/Flakes

Calcium Treated Fluids
Heavy Clear Brines
Freeze Point Depression
Vapor Pressure
Equalization
Flocculated Water
Systems

Calcium Hydroxide

Ca(OH)
2


Soft White Powder

Calcium Treated Fluids
Alkalinity Control

Magnesium Chloride

MgCl
2


White Crystals

Stability in Complex Salt
Zones

Potassium Chloride

KCl

White or Pink Crystals

Potassium Treated Fluids

Potassium Hydroxide

KOH

White Pellets or Flakes

Alkalinity Control in K
+

Fluids

Sodium Bicarbonate

NaHCO
3


White Powder

Treatment for Cement
Contamination

Sodium Chloride

NaCl

White Crystals

Brine Formulation,
Evaporate Drilling, Freeze
Point Depression,
Bridging Agent

Sodium Hydroxide

NaOH

White Beads or Flakes

Alkalinity Control,
Suppression of Ca
2+

Solubility Suppression of
Corrosion, Product
Solubilization Soluble
Sulfide Control

Sodium Sulfite

Na
2
SO
3


White Crystals

Oxygen Scavenger

Zinc Carbonate

ZnCO
3


White Powder

Soluble Sulfide Precipitant

a
Descriptions of these and other conditioning chemicals are found in the Ava Product Data Book



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7.5 WATER-BASED SYSTEMS

Some of the most common fluid types and systems used by Ava are described in the following
text. This does not constitute a complete list of our systems. It is often necessary to alter water-
based system composition, to suit specific applications. Often completely new systems are
designed to perform specialized functions. The fluid formulations and operational aspects
described in this text are often changed and expanded upon. This takes place regularly when a
program is written for a particular well.


7.5.1 Mixing, Converting and Displacing

There is usually a preferred sequence for mixing the various water-based fluid components. The
system descriptions attempt to explain the reasons for this. When new chemicals are introduced
or concentrations are changed, it is always a good idea to pilot test first. Youre nearest Ava
Technical Services Department is equipped with good database and library, manned by
experienced drilling fluid Engineers. It is their job to provide answers and suggestions to
questions you might have regarding systems, components, compatibility or problems.

Some of the drilling fluid systems described here, such as Gyp or Salt are often fabricated by
converting existing systems as drilling proceeds. Here again pilot testing is recommended.
This will indicate a need for alternate chemicals or procedures.

It is always a good idea before converting any systems to ensure the proper equipment is
available and functioning. All necessary chemicals including contingency chemicals should be
available and ready to mix. There should be a written plan of action. All personnel involved,
including the Drilling Engineer, Driller, Derrickman and Roustabout should understand their role in
the procedure, step-by-step. When converting clay / water systems where flocculation, viscosity
humps or other changes are expected keep accurate records of properties, especially suction
tank values. Try to keep the system properties as even as possible. Chemical analysis made on
an uneven system makes subsequent treatments, concentrations and procedures a stab in the
dark at best. If the suction tank properties do begin to fluctuate the driller is usually able and
willing to slow the pump down long enough to adjust chemical addition rates and the
corresponding suction tank properties.

Drilling fluid systems are usually displaced to alternate systems just prior or just after drilling out a
casing shoe. Usually displacements are not conducted while drilling ahead. In most cases the
displacement procedure is discussed between the operator and Ava prior to drilling the well and
included in the Drilling fluid program.


7.5.2 Spud Muds

Spud muds are used to drill surface holes. Usually the main function of a spud mud is to clean.
Surface hole bits have bigger teeth generating bigger cuttings. Because surface holes are of such
large diameter (up to 36"), annular velocities are low, even at maximum pump rates. This means
that spud mud viscosities are usually high. When choosing a spud mud, the two main
considerations are the formation pressure gradient and the availability and type of make-up
water. Often surface formations are underpressured, lost circulation is a problem and fluid
densities must be kept low. Occasionally abnormal pressures or overburden stresses are
encountered on top hole. In these cases, the spud mud must retain the ability to suspend Barite.

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Spud mud systems and components must conform to certain criteria. The products must be able
to be mixed rapidly, using simple recipes, and the systems must be economical. The amount of
material usage should be minimized, especially on floating rigs where deck space is limited and
returns are directed to the sea floor.

Make-up water analysis is always essential prior to mixing any fluid system; especially spud
muds. Contaminants such as calcium or magnesium must be precipitated before many
commercial additives can be expected to perform properly.

On land, top hole is usually drilled with one of the following spud mud systems:

1. Native Solids
2. Bentonite/Lime
3. Bentonite
4. Extended Bentonite

The funnel viscosity of these systems is usually maintained at 40-60 s/l until casing depth is
reached, where it might be raised to 80-120 s/l to facilitate running casing. In some areas, its
advisable to spud with, and maintain a viscosity above 150 s/l until the 11 and 9-inch drill collars
are drilled down. The improved cleaning characteristics reduces time spent laying down big
collars - when difficulty is encountered making connections in incompetent formations such as
gravel. When lost circulation or gravel is encountered, the viscosity should be raised to 150 s/l or
higher. Other important properties include pH, alkalinity and density. Spud muds are often
discarded after use.

Native solids systems are used in areas where "mud making" clays are encountered. The well
is spudded with fresh water, and viscosity builds naturally. Caustic, Lime or Bentonite may be
added to these systems as required to increase the viscosity. The wall-building and suspension
characteristics of these fluids are poor.

Gel/Lime slurries are often used on shallow surface holes. Usually about 60 kg/m
3
of Bentonite
is added to fresh water until a funnel viscosity of 35 - 40 s/l is obtained. The system is flocculated
with small quantities of Lime (Ca(OH)
2
) through a chemical barrel when a viscosity increases is
required. The ratio of Gel to Lime should be about 35:1. The mistake most often made with this
system is that Lime is added before enough Bentonite has been added. This leaves excess
calcium in the system, inhibiting the yield of subsequent Bentonite additions.

Bentonite and extended Bentonite systems are also used for land-based drilling, usually when
the surface interval is longer than 2 - 3 days. The procedure is to increase and maintain the pH of
fresh water at 9 with about 0.75 kg/m
3
Caustic Soda. Bentonite is added to the desired funnel
viscosity allowing time for hydration. When an extending polymer such as Avabex is used 0.5 kg
is mixed with each 10 sxs of Bentonite.

The advantages of these systems include; good cleaning and hydraulics, better wall plastering
and hole stability, lower solids concentrations and higher ROP's. If the low gravity solids content
is kept low enough (less than 150 kg/m
3
) then the fluid can usually be used on the next interval.

Offshore, top hole is usually drilled with seawater and viscosity sweeps. Continuous
viscosification becomes expensive since, when drilling without a riser, there are no fluid returns to
the rig. Some Operators can recover sweep fluid through an airlift system, stung into the TGB.
Returns, including cement, and sweep effectiveness can then be analyzed at the header box,
sweeps can be recovered and surface gas can be monitored.

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Initially, sweeps should be large enough to cover 10-15 m of annulus and they should be pumped
every 15m or so. When drilling through permafrost or gas hydrate baring formations, sweeps
should be chilled first. If coolers are not available, viscosifiers should be added to cold seawater
just prior to pumping the sweep. It is advantageous and cost effective to use readily dispersible
polymers such as Avagum (Guar Gum) for this purpose.

Since cuttings can't normally be seen, the ultimate frequency and size of viscosity sweeps should
be dictated by hole conditions. Drilling parameters indicating insufficient cleaning include
excessive:

1. Rotary Torque
2. Hole Drag
3. Pump Pressure
4. Fill on Connections

It is imperative that good communication between the Mud Engineer and Driller be maintained at
all times during surface hole. The Driller is the first man on the rig to know when the drilling fluid
Engineer's spud mud strategy needs re-evaluation.

Occasionally continuous viscosification is necessary when flowing sand is present. If squeezing
formations remain persistent, densification of the fluid can be beneficial. Upon completion of the
interval, "bottoms up" is usually circulated several times. The hole is then displaced with 1.5

- 2
times gauge volume, with viscosified and/or densified fluid. This is done to keep solids suspended
or to maintain borehole stability while logging and running casing.

Bentonite-based systems and sweeps are often used in a variety of ways to spud on and
offshore wells. Drill water / bentonite systems can be used. Sometimes they are flocculated with
Lime, or extended with a polymer such as Avabex. More often, PHB and seawater are blended
just prior to being pumped. This promotes flocculation and reduces the required amount of drill
water. (It also increases the fluid loss). Table 7.13 shows a typical drill water / Bentonite
formulation. Other variations of clay-based spud muds which have been used in offshore
applications include Bentonite / CMC and Attapulgite or Sepiolite systems.


TABLE 7.13 BENTONITE / SEAWATER SPUD MUD

ADDITIVE

PRODUCT NAME

CONCENTRATION
kg/m
3

Water
NaCO
3
Soda Ash 1.0 - 3.0
NaOH Caustic Soda 1.0 - 2.0
Bentonite Avagel 110.0 - 140.0
Yield for several hours

Add Seawater and small amounts of Caustic
Typical Properties:
Funnel Viscosity 100 - 150 sec/L
Yield Point 25 - 40 pa
pH 8.0 - 8.5


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Guar systems are often used to drill top hole on land based and offshore locations. Guar is
mixed with relative ease (10 - 15 min/sack), providing good properties with an optimum of
hydration time, usually 1 - 2 hours. Guar provides good suspension properties at low
concentrations and reasonable cost. Guar also provides some filtration control characteristics.
Guar gum is insensitive to pH fluctuations, salt and multivalent cations. Guar systems being
stored should be kept cool and treated with a bacteriacide. Table 7.14 shows a typical guar
formulation.


TABLE 7.14 GUAR SPUD MUD

ADDITIVE

PRODUCT NAME

CONCENTRATION
kg/m
3

Water
NaOH Caustic Soda 0.5 - 1.5
Guar Gum Avagum 8.0 - 15.0

Yield 1 - 2 Hours

Typical Properties:
Funnel Viscosity 100 - 200 sec/L
Yield Point 25 - 40 pa
pH 8.0 - 9.0


Some Operators especially in Arctic offshore areas use Xanthan Gum systems. There are three
important reasons why this is so:
1. Transportation costs to the Arctic are high. It is almost as cheap to viscosify a
cubic meter of seawater with 5 kg of XC Polymer as it is to use 100 kg of
Bentonite.

2. Arctic spud muds should be chilled prior to pumping. Warm spud mud melts the
permafrost, resulting in gas hydrate release or washouts. Systems and sweeps
built with Xanthan Gum are less apt to plug mud coolers than systems built with
Guar Gum.

3. Xanthan is more dispersible in cold seawater than many other products. (With a
good shearing hopper, it can and has been mixed at 1 min/sack). This is
important because, if continuous viscosification is required, Xanthan must be
added to new, cold seawater and pumped away immediately. There is no sense
pumping any fluid once its above 3 - 4C.


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TABLE 7.15 VISCO 84 SPUD MUD (SWEEP)

ADDITIVE

PRODUCT NAME

CONCENTRATION (kg/m
3
)
Water
Xanthan Gum Visco 84 4.0 - 8.0
NaOH Caustic Soda 0.5 - 1.5

Typical Properties:

Funnel Viscosity 45 - 200 sec/L
Yield Point 10 - 30 pa
pH 7.5 - 9.0


Table 7.15 provides a recipe for a typical Xanthan (XCD) sweep. When continuously viscosifying
with Xanthan the concentration and mixing rate is best determined at the well site. It is dependant
on both the required yield point and the pump rate.


7.5.3 Low Density Fluids

Low density fluids are sometimes called gas-based or reduced pressure drilling fluids. The
original purpose of these fluids was either to avoid loss of circulation or reduce the amount of
water lost into production zones. Improved rates of penetration and longer bit life soon became
well-known secondary benefits. These systems can be classified as follows:

1. Gas or Air
2. Mist / Foam
3. Stiff / Stable Foam
4. Aerated drilling fluid

Dry gas drilling was first patented in 1866 and is still used in many areas today. When drilling
with gas or air, enough volume must be supplied to generate annular velocities in the range of
900 m/min. Care must be taken to avoid the risk of down hole fires and explosions.

The intrusion of formation water into the wellbore (above 0.3 m
3
/h), creates problems resulting
from the aglomeration of sticky cuttings. Mud rings or seal rings begin to form in the annulus. The
injection of small amounts of drilling fluid or water containing a foaming surfactant results in a mist
or foam drilling fluid. The foaming surfactant mixes with the formation water. This increases
carrying capacity, permitting the removal of water from the hole at lower annular velocities. As
much as 80 m
3
/h of water can be removed with foam.

The first stable foam drilling fluids were developed by the U.S. atomic energy commission for
use in drilling large diameter holes. The original recipe included: water, Soda Ash, Bentonite,
Guar Gum and a foaming agent. Subsequent recipes are more resistant to contamination. Stiff
foam fluids have the consistency of shaving cream. They are used when: an air drilling operation
encounters a water flow, for clean out and remedial work. For drilling permafrost, foam has low
head conductivity and low heat capacity, or as the primary drilling fluid. The composition of foam
at any temperature can be expressed as a liquid volume fraction. The particle lifting ability of
foam increases as liquid volume fraction decreases.

Phillips Petroleum first used aerated drilling fluids in 1953. Various systems have been
employed to inject air into the drilling fluid and thereby reduce hydrostatic head. These include,
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injecting air into the standpipe, injecting air into the annulus; and using a dual drill string-one
within the other.

Often the company providing the compressors and other air drilling equipment helps in supplying
air drilling fluid chemicals. The Mud Engineer should be available to monitor corrosion rates,
supply proper corrosion inhibition chemicals and maintain a specified drilling fluid system ready
for instant mud-up. Although air drilled holes are usually close to gauge, often the dry formation
absorbs a substantial amount of drilling fluid after mud-up. The drilling fluid engineer should
usually have 30 - 40% excess volume available in the event that this happens. The rate of loss
should also be monitored to ensure that it decreases with time. If not, lost circulation material
must be added. Some areas are notorious for exhibiting stress relief problems (sloughing) 2-3
days after mud up. Often it is a good idea to have viscous sweeps available, should this occur.


7.5.4 Clear Water Systems

Many land-based operations employ a clear-water system under the surface casing shoe to a
specified mud-up depth. The advantages of these systems are economical: a cheap system and
a rapid rate of penetration. The application of clear-water systems is limited to areas of normal
formation pressure, and where borehole stability is not a major concern.

There are three methods of drilling with clear-water. The easiest one involves using the water
available at the location by itself. Needless to say, this type of drilling uses copious volumes of
water. However, where lost circulation is so severe that it can't be remedied this could be a viable
option. Either a good pumping system or many water trucks supply water to the suction tank, and
drilling "blind" proceeds with no returns to surface

Sodium Acid Pyrophosphate (SAPP) is a strong deflocculant. SAPP is discussed in chapter 5.
SAPP / water fluids are used to drill under the surface casing shoe, usually on shallow wells to
minimize mud rings and bit balling in clay formations. SAPP systems are only recommended for
drilling up to about 600 m of open hole. Circulation is established through the sump, which should
contain at least 100 m
3
of water. Enough Sodium Bicarbonate or SAPP should be added initially
to treat out the cement between the float and shoe and in the rat hole. One kg or one viscosity
cup of SAPP should be added to the drill pipe on each connection. SAPP can also be added to
the suction put at 1 kg for each 10 m of new hole drilled. If mud rings or bit balling become
severe, a SAPP slug may be pumped. This involves mixing about 20 kg of SAPP into a chemical
barrel and adding it as close to the pump suction as possible.

While drilling with SAPP the density should be maintained as low as possible with regular
additions of water. SAPP water systems are not normally used to make up subsequent drilling
fluid systems.

Flocculated water systems are used in many areas where conditions permit deeper (up to 2000
m) water drilling. The main advantages of flocculated water include:

1. Inexpensive
2. Rapid ROP's
3. Low solids, non-abrasive
4. Easy Maintenance
5. Resistant to Contamination
6. Sump water may be reclaimed for building drilling fluid

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When drilling with flocculated water, polymers are added to the circulating system at surface,
usually near the shale shaker. These polymers become attracted to drilled solids, causing them to
aggregate. The increased effective diameter of the aggregates promotes rapid settling. The
objective of this system is to supply completely clear water to the pump suction.

Several types of flocculant are available. Typical chemical concentrations and fluid properties for
this system are outlined in Table 7.16. Calcium Chloride is used to increase the effectiveness of
the flocculant. Other salts may also be used, if required for borehole stability or in environmentally
sensitive areas:

Potassium Chloride 10 - 30 kg/m
3


Diammonium Phosphate 8 - 15 kg/m
3


Ammonium Sulfate 8 - 15 kg/m
3


Gypsum 2 - 3 kg/m
3



TABLE 7.16 FLOCCULATED WATER SYSTEM

ADDITIVE

PRODUCT NAME

CONCENTRATION (kg/m
3
)

Polymer Flocculant AvapolJ 1-2 L/m
3
of 50% solution
CaCl
2
Calcium Chloride .5 - 1.5 kg/m
3
(100 - 300 mg/l Ca
2+
)
Ca(OH)
2
Lime pH: 9.5 - 10.0

Typical Properties:

Fluid Density 1 000 - 1 020 kg/m
3

Funnel Viscosity 27 - 28 s/l
pH 9.5 - 10.0
Calcium 100 - 300 mg/l


The sump should be large enough to accommodate 300 - 400 m
3
of water. An earthen dyke is
usually constructed up the middle of the sump. This forces the flowing water to channel,
increasing the available settling time. Solids may also be flocculated in the rig tanks; however,
this substantially increases the chemical requirements.

Initially 500 - 800 kg of CaCl
2
are added to the drilling water. Cement from the shoe joint and rat
hole is not treated out. Ca(OH)
2
is added with the initial treatment of CaCl
2
to raise the pH to 9.5 -
10.0. This usually requires 200 - 400 kg of Lime. This pH level minimizes corrosion and
maximizes polymer solubility. In some areas the system is run at neutral pH, resulting in better
gauge holes. In these systems gypsum is substituted for lime. Normally 1 kg of the flocculating
polymer is added to 15 - 20 l of diesel fuel and stirred. This mixture is then added to a chemical
barrel full of water. It's best if the chemical barrel is equipped with an electric agitator. The
flocculant mixture should be added at the shaker continuously while drilling, at a rate of 1 kg for
each m
3
of new formation drilled. Maintaining the system usually requires the addition of 50 - 100
kg of CaCl
2
and 25 - 75 kg of Lime or Gyp each 8 hours. 15 - 30 m
3
of fresh water are also added
each 8 hours.

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If the water at the pump suction becomes dirty or cloudy the usual procedure is to add
approximately 200 - 300 kg of CaCl
2
over one circulation. If this treatment fails, pilot testing
becomes imperative. Varying amounts of CaCl
2
or flocculant are added to a glass jar containing
the cloudy drilling fluid. Observations are made to discern which product or combination
decreases particle-settling time most efficiently. If this fails, the next step is to try a different type
of flocculant.

Care should be taken to ensure that too much flocculant isn't added. When this occurs, "flocs"
can be observed in the returning fluid, upstream of where new flocculant is being added. This
indicates that flocculation and settling is occurring in the annulus. Further considerations when
running flocculated water systems include:

1. If using diammonium phosphate or ammonium sulfate, all of the cement must first be
treated out with Sodium Bicarbonate. In this case, to avoid the release of free
ammonium, the pH should be maintained below 7.8.

2. Annular velocities should be maintained at 40 - 50 m/min. Surveys should be made off
bottom when possible. It is advisable to circulate 15 - 20 min. prior to stopping tools to
survey, trip or repair.

3. Fill on connections usually indicates the need to change to viscosified drilling fluid. The
clear-water drilling interval can often be extended if viscous sweeps are pumped
intermittently.

4. If the sump water is to be used for future make-up water, Calcium Chloride and Lime
additions should be discontinued 6 - 8 hours prior to mud-up depth. Selective flocculant
additions can be made right up to mud up depth. The calcium concentration of the sump
water should be lowered to 60 - 80 mg/l prior to initiating Bentonite additions. Often a
concentrated batch of prehydrated Bentonite is kept on standby ready to blend with fresh
water, if an "instant" mud-up is required.


7.5.5 Gel-Based Systems

Gel-based (Bentonite) drilling fluids systems are by far the most common systems used for land-
based drilling. Since their inception in the 1920's, they have been used throughout the world to
successfully drill through many types of formations and conditions. Ongoing research and
development has provided a diverse array of proven complimenting components and chemicals
for these systems. Hence, Gel-based systems may be modified to address one, or several
specific drilling fluid functions. Gel-based drilling fluids often provide the most economical
combination of desired characteristics, imparting good suspension properties and lifting capacity,
favorable shear thinning characteristics, and good fluid loss and wall building properties.

In a fresh water environment, hydration forces are strong enough to separate natural Bentonite
aggregates. Separation into individual unit layers is possible. Unit layers are about 10 angstroms
thick and between 100 and 1 000 angstroms square. The shape of these hydrated platelets
imparts resistance to flow or viscosity to a clay suspension. When a shearing force (movement) is
applied to a Bentonite suspension, the platelets align themselves in a direction parallel to the
force. Resistance to flow then decreases, explaining the shear-thinning nature of Bentonite
suspensions. This thin-flat shape also provides good fluid loss characteristics to the suspension.
Because the clay platelets have surface charges, they align themselves to positions of minimum
free energy when the suspension is at rest. This accounts for the thixotropic properties exhibited
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by Bentonite suspensions. The preceding mechanisms and terminology are explained in greater
detail in the Clay Chemistry chapter.

Bentonite systems have many permutations, including systems, which incorporate various
borehole stability components. There are three types of basic Bentonite systems:

1. Non-Dispersed Bentonite (Gel Chemical)
2. Low Solids (Extended Gel)
3. Dispersed Bentonite (Lignosulfonate)

Please note that the terms Non-Dispersed and Dispersed refer to the degree of imparted
deflocculation in a Gel suspension. When the Industry talks about a "dispersed" system, it
actually means a deflocculated system. Accurate colloidal chemistry terminology would replace
the word dispersed with deflocculated. (When dry Bentonite aggregates hydrate and disperse in a
premix tank the solution becomes thicker - not thinner.) When Lignosulfonate is added, clay
particles dissociate, the suspension is deflocculated and it becomes thinner. Similarly, the
Industry term "non-dispersed" refers to a system, which has not been deflocculated with a
thinner. These terms are discussed in greater detail in the Clay Chemistry chapter.

Non-Dispersed Bentonite systems are often called Gel Chemical systems. Table 7.17 lists the
components, concentrations and properties typical of Gel Chemical fluids.


TABLE 7.17 NON-DISPERSED BENTONITE SYSTEM

ADDITIVE

PRODUCT NAME

CONCENTRATION
kg/m
3

Freshwater
NaCO
3
Soda Ash 1.0 - 3.0
NaOH Caustic Soda 0.5 - 0.75
Bentonite Avagel 45 - 75
CMC CMC 1 - 6

Typical Properties:

Funnel Viscosity Above 35 s/l
Density 1,050 2,000 kg/m
3

PH 9.0 - 10.0
Fluid Loss 3 - 10 ml/30 min
Calcium Less than 100 mg/l


Complimenting components for these systems include most of the water-soluble products
outlined previously in this chapter. The mixing order of this system is important. For best results,
fresh water should be used. Excessive salt (>5 000 mg/l) and hardness interfere with the
hydration and effectiveness of the Bentonite. Soda Ash should be used to treat the calcium in the
make-up water to less than 40 mg/l. The pH should be adjusted to 9.5 - 10.0 prior to adding
Bentonite. The Bentonite should be added slow enough that balling and clogging is eliminated.
The initial yield depends in part on the quality of the surface equipment. Normally the slurry
becomes thicker with time and agitation.

Usually 60 - 70 kg/m
3
of quality Bentonite will produce a slurry with a funnel viscosity of 38 - 42
s/l. This concentration provides a natural fluid loss of approximately 12 - 15 ml/30 min.
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The yield point of this system should be maintained at a sufficient value to provide effective hole
cleaning characteristics and Barite suspension with additions of Gel as required. In an
unweighted system, the plastic viscosity value in mPas is usually about twice the value of the
yield point in Pa. The plastic viscosity (PV) increases as the solids concentration in the system
increases. The PV value should be maintained as low as possible by running proper solids
control equipment and by dumping and dilution. The pH should be maintained between 9.0 and
10.0 with additions of Caustic Soda. This aids in hydrating the Bentonite, reducing corrosion
rates, and minimizing the solubility of contaminants. The fluid loss may be readily lowered with
CMC polymer providing contaminating electrolytes are not present in the system. The calcium
content should be kept below 80 mg/l with Soda Ash. A residual concentration of soluble calcium
(30 - 80 mg/l) left in the system insures that carbonate related problems will not develop. When
chloride concentrations exceed 5 000 mg/l it is advisable to prehydrate the Bentonite prior to
adding it to the active system.

When drilling ahead with this system, appropriate volumes of fresh water and Bentonite should be
added to the system to avoid dehydration, especially as the system temperature increases. A
Non-Dispersed system is not a low solids system; it is prone to rapid solids build up, especially at
high rates of penetration. Therefore the solids content should be monitored closely and controlled
properly. Once the average particle size degrades to beyond the capabilities of the available
solids equipment, expensive whole fluid dumping and dilution becomes imperative.

Because the surfaces of Bentonite platelets are electrically charged, this system is inclined to
react unfavorably to many types of ionic contaminants. These include most salts, which are
encountered while drilling through evaporate formations and the acid gasses, H
2
S and CO
2
.

It should be noted that the physical and chemical conditions, which promote the most efficient
dispersion of Bentonite particles and the best control of Non-Dispersed Bentonite system
properties, are:

1. Fresh Water
2. High pH Conditions
3. High Mechanical (Shear) Energy
4. Low Calcium Concentrations

These same conditions are advantageous to the hydration and dispersion of formation shales and
clays. Often asphaltic derivatives or PHPA are added to these systems to impart shale inhibition
properties.

Low Solids Systems are often referred to as Extended Gel Systems. These systems have been
used successfully in various areas since the early 1960's. They may be used in most areas where
a Non-Dispersed system can be used. The most important advantage of Low Solids systems is
that they promote faster rates of penetration (ROP). They are also less abrasive and easy to
maintain. Low solids systems exhibit good rheological properties. They usually contain no more
than 4-7% solids by volume.

The system employs an anionic polymer of medium to high molecular weight. This polymer
attaches to positive edge sights on two or more clay plates, linking or bridging the plates together.
This results in an increase in viscosity, caused by a soluble molecule and not an insoluble
particle. Therefore a desired degree of viscosity in a given suspension may be achieved with
fewer solid particles. This markedly improves ROP's where the system is used. Extending
polymers are discussed in greater detail in the chapter on Polymer Chemistry. Table 7.18 outlines
the products, concentrations and properties of Extended Gel systems. Note that premium quality
Bentonite is used.
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TABLE 7.18 LOW SOLIDS (EXTENDED GEL) SYSTEM

ADDITIVE

PRODUCT NAME

CONCENTRATION (kg/m
3
)
Freshwater
NaCO
3
Soda Ash 1.0 - 3.0
NaOH Caustic Soda 0.5 - 0.75
Bentonite Avagel 30 - 60
Extending Polymer Avabex .07 - .15
CMC Carboxy Methyl Cellulose 1 - 6

Typical Properties:

Funnel Viscosity 35 - 60 s/l
Yield Point 7 - 15 Pa
Plastic Viscosity 10 - 25 mPas
Density 1 060 - 1 100 kg/m
3

Solids 4 - 7% (Vol)
pH 9.0 - 10.0
API Fluid Loss 2 - 8 ml/30 min
Calcium Less than 100 mg/l

The material mixing order for Extended Gel systems is similar to the previously discussed Non-
Dispersed system. The extending polymer is mixed through the hopper along with the Bentonite.

The maintenance and value range of the pertinent properties including YP, pH, fluid loss and
calcium concentration is also similar to the Non-Dispersed gel system. More attention is usually
paid to fluid density, solids content and solids control efficiency when running these systems.
Generally an upper density limit of 1100 kg/m
3
(about 6-10% volume solids) is tolerated before
dumping and diluting are initiated.

Contaminating ions and acid gasses are detrimental to the performance of Low Solids systems.
When peptized or extended Bentonite is used with extending polymers, there is a risk that flow
properties especially gel strengths will be adversely affected (reduced). This was especially so
with the vinyl acetate, maleic acid (VAMA) co-polymer used until the middle 1980's, where over
treatment of polymer would drastically reduce the viscosity. The acrylate co-polymers used as
extenders today don't actually cause a viscosity hump, but when they are used in conjunction with
peptized gel, it is difficult to attain sufficient gel strengths or satisfactory low-end rheology.

Dispersed (Lignosulfonate) Systems were first used on the early 1950's to control the flow
properties of Lime Muds. Today these systems have gained widespread acceptance, they are not
just limited to calcium-based systems. Lignosulfonate systems are the most common systems
used today in the Gulf of Mexico. They are usually the most economical systems to use in
environments where a contaminant or high temperatures would adversely affect the rheological
properties of a Non-Dispersed system. Lignosulfonate systems make gel-viscosifed, water based
fluids rheologically tolerant to virtually every type of contaminant. This includes reactive clays,
high solids, salts, hardness, acid gasses and moderate temperatures. They can be formulated
from both fresh water and seawater.

Other advantages are realized when Lignosulfonate systems are used. These include:

1. They inhibit shale hydration at higher concentrations.
2. They impart good filtration properties to a system.
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3. They are easy to maintain and compatible with most common additives. (Most
clay-water systems can be easily converted to Lignosulfonate systems).
4. They are inexpensive.
5. They are good emulsifiers at up to 10% oil content.

Lignosulfonates are high molecular weight anionic polymers. They have a relatively high negative
charge density. They function by bonding to positive edge sights on clay platelets. This effectively
causes the clay plates to have an overall negative charge. Thus individual clay plates repel.
Further discussion on the topics of deflocculation and Lignosulfonates is presented in the Clay
Chemistry chapter (4) and the Polymer Chemistry chapter (5). Table 7.19 shows the components
concentrations and properties typical of Lignosulfonate systems.

TABLE 7.19 DISPERSED (LIGNOSULFONATE) SYSTEMS

ADDITIVE

PRODUCT NAME

CONCENTRATION (kg/m
3
)

Fresh or Seawater
NaOH Caustic Soda 0.5 - 6.0
Bentonite Avagel 70 - 100
Lignosulfonate Avafluid G71 2 - 30
Polyanionic Cellulose Policell 1 - 6

Typical Properties:

Funnel Viscosity 38 - 150 s/l
Yield Point 7 - 20 Pa
Plastic Viscosity 15 - 50 mPas
Density 1 100 - 2 200 kg/m
3

pH 10.0 - 10.5
API Fluid Loss 1 - 10 ml/30 min


Lignosulfonate systems can be built as such or they can be converted from non-dispersed clay /
water systems. Usually Gel / Chemical systems are converted to Lignosulfonate systems prior to
encountering an expected contaminant. The properties of Lignosulfonate systems may be
modified with a wide range of additives to suit most drilling conditions.

The concentration of Lignosulfonate depends on the type and expected severity of the
contaminant and the concentration of reactive clays in the system. If only minor stringers of
anhydrite are expected 2 - 4 kg/m
3
is usually sufficient to deflocculate. If massive anhydrite or salt
contamination is expected 10 - 20 kg/m
3
will be necessary to control both the flow properties and
the fluid loss. In extreme cases, 20 - 30 kg/m
3
of Lignosulfonate is used in a system. High
concentrations such as these are used to inhibit temperature-induced dispersion of formation
clays, minimize HTHP fluid loss values and treat extremely severe contamination. Often a Gel
Chemical system is treated with 10 - 12 kg/m
3
of Lignosulfonate before drilling into an H
2
S zone.
The excess Lignosulfonate serves to dampen the flocculating effects of both the H
2
S and the
ZnCO
3
scavenger, if it is being used. Often the best method of converting to a Lignosulfonate
system is to simply watch closely and maintain the desired rheological properties in the suction
tank, either with additions of Lignosulfonate or Bentonite. This becomes imperative if the severity
of the contaminant is unknown. If the contaminant is an electrolyte, Bentonite will have to be
prehydrated first. Both Caustic Soda and an alcohol-based defoamer should also be available
when adding Lignosulfonate, since it is acidic and has a tendency to foam. Usually Lignosulfonate
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should be mixed about 5:1 or 6:1 with Caustic. This ratio will decrease if CaSO
4
is the
contaminant.

Once the system is built, it is extremely simple to maintain. The YP and gel strengths are
controlled with PHB or Lignosulfonate as required. A lower YP : PV ratio and a higher n value
(shear-thinning index) are to be expected. This is because most of the clay particle associations
have been broken chemically leaving less or none at all to be broken by mechanical shearing
forces. Thus the system is not very shear thinning. Usually PAC polymers are added if additional
fluid loss control is required. The higher degree of substitution in these polymers makes them
more tolerant to the various contaminants the system is being used to drill through.

The acidic nature of most Lignosulfonate products requires that substantially more Caustic be
added to the system. This requires close monitoring. (pH 10.0 - 11.0 is acceptable). If the pH is
allowed to drop, flocculation and foaming often occur. If the pH becomes too high, free hydroxyls
and/or sodium ions may lead to increased dispersion of certain reactive formation clays,
promoting borehole instability. A permutation of Lignosulfonate systems uses a modified tannin
extract (DESCO) to deflocculate. DESCO works well in neutral pH environments (7.9 - 8.3).

Lignosulfonate systems have disadvantages. These can usually be overcome if one is aware that
they exist. Because Lignosulfonate systems have such a good resistance to drilled solids
contamination, ROP's may be lower if drilled solids are high. Often they are used in tertiary
formations where controlled drilling is practiced, so the reduction in ROP isn't a concern. Fluid
temperature can affect the performance of these systems because when Lignosulfonates are
degraded by heat, both H
2
S and CO
2
may be produced. The temperature limitations of
Lignosulfonate systems may be extended with lignins, resins and asphaltic derivatives.


7.5.6 Salt Saturated Systems

Salt Saturated systems gained widespread use both in the Permian Basin of West Texas and in
the Gulf Coast in the middle 1930's. These fluids were developed for drilling through salt beds
and salt domes. When extensive salt intervals are penetrated with an undersaturated solution,
the salt formation tends to solvate, or enter the solution often resulting in severely "washed-out"
holes. The poor performance of Bentonite in salty environments led to the application of
attipulgite clays as viscosifiers in 1937. The inferior cake-building characteristics exhibited by
these clays resulted in drilling problems including differential sticking and sloughing shale. Starch
was soon found to be the most economical material for improving cake characteristics.

Not all drilling fluid systems containing salts have to be saturated. Systems are often used which
are formulated from produced brines or seawater exhibiting various degrees of salinity. Some
systems are formulated with specific salt concentrations, optimized to control bentonitic
formations; KCl systems are discussed later in the chapter. The salinity of water-based systems
is sometimes increased to enhance SP or resistivity log results, or to freeze depress drilling or
packer fluids.

The basic formulation, concentrations, and properties for a salt saturated system are shown in
Table 7.20. This formulation is often modified to suit specific purposes. Many components can be
substituted with more appropriate products if required. These include: PAC, Guar, PHB,
Attipulgite, Lignosulfonates, Lignites and Resins.

Usually an existing water / clay system is converted to a salt saturated system prior to penetrating
the evaporate interval. When salt is added to these systems the suspended clays invariably
become extremely flocculated. Pilot testing can provide a good indication regarding the
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necessary procedures, in terms of chemicals required while converting, mixing order, and how
many circulations it will take.


TABLE 7.20 SALT SATURATED SYSTEM

ADDITIVE

PRODUCT NAME

CONCENTRATION
(kg/m
3
)

Freshwater
NaCl Sodium Chloride 350 - 360
NaOH Caustic 1.5 - 2.0
Drilling Starch Victosal 5.5 - 17.0
Xanthan Gum Visco XC 84 2.0 - 4.0
or
HEC Hydroxyethyl Cellulose 2.0 - 4.0

Typical Properties:
Yield Point 5 - 8 Pa
Plastic Viscosity 10 - 12 mPs
pH 9.0 - 10.0


Prior to adding the salt, it is usually necessary to dilute the existing system back with water,
sometimes as much as 40%. Ideally the funnel viscosity should be lowered to about 35 sec/l, if
hole conditions permit. Caustic Soda may be added at this time. The salt should be added next.
Be sure to allow enough tank volume for the addition of the salt.

Saturated salt solutions require about 320 kg/m
3
NaCl depending on temperature. For each cubic
meter of fresh water to be saturated, about 360 kg of NaCl should be added. This will result in a
volume increase of about 140 liters. In a saturated NaCl solution the salt will account for about
12% of the final volume. Refer to the salt tables in the appendix of this manual.

Care should be taken to monitor the suction tank viscosity. If it becomes excessive, appropriate
amounts of thinner should be added. Remember a viscosity hump occurs as the clays become
flocculated. Once enough salt has been added to initiate aggregation the viscosity will decrease.
When the salt has been mixed, Starch can be added at about 10 - 15 min/sack. The rheology
should again be monitored when mixing the starch. If fish-eyes or screen blinding is evident,
reduce the rate of starch addition to 20 - 30 min/sack.

When drilling salt formations, plastic yielding of the salt may be encountered. At shallow depths,
the deformation may be slow enough that the hole can be kept in gauge by reaming. Slight under
saturation can sometimes prove beneficial, if the brine dissolves the salt, compensating for the
plastic flow. However, if the salinity is too low, too much salt is dissolved, resulting in excessive
hole enlargement.

In some cases, an increase in hydrostatic pressure can overcome the plastic flow without the risk
of dissolving formation salt.

Because salt sections are mechanically weak, some washouts that occur can be attributed to
mechanical erosion rather than chemical solution. To counter this, annular velocities should be
kept fairly low until the BHA has past the salt zone. Nozzle velocities should be restricted to less
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than 95 m/sec by using larger nozzles. The consequent reduction in hydraulic horsepower at the
bit should not affect drilling rates due to the softness of the salt.

The solubility of salt in water increases slightly with increasing temperature. Care should be
exercised when using a saturated salt system, as the brine may be saturated at surface
temperature, but may be under-saturated at bottom hole temperature. When a saturated salt
system is being used, it is advisable to maintain at least 10 - 15 kg/m
3
of excess salt in the
system to ensure saturation at down hole temperatures. The chloride concentration should be
maintained at 190,000-193,000 mg/l, and salt crystals should be evident at the shaker.


Temperature Salt to Saturate
21C 360
26C 362
32C 363
37C 365

Saturated salt systems can be thinned with Lignosulfonates for the short term, but this may not
provide long-term results. A reduction in viscosity is best achieved through a reduction in the
system solids content. In some instances, small additions of PAC or CMC (0.75 - 1.5 kg/m
3
) can
be beneficial in deflocculating and thinning a salt saturated mud. If the diluent is not saturated salt
water, undersaturation of the fluid will occur. If it is necessary to build volume or reduce viscosity
while salt is being drilled, a small stream of undersaturated water can be run into the shaker box
or some other point ahead of the shaker. Dissolving the salt cuttings will then saturate the water.
The shaker may also be by-passed to collect drilled salt in the tanks. Water is slowly added and
the salt cuttings gunned so that they dissolve. (This procedure is permissible only if there are no
accumulations of solids in the pit.)

Saturated salt water systems may require a bactericide. On occasion, the fluid loss will increase
rapidly and not reduce for any appreciable period of time after a normal starch addition. Such a
system may not have fermentation odors, but frequently, the addition of a biocide will result in re-
control of the fluid loss properties with normal quantities of starch.

Any system, which is saturated with a given ion, has a reduced capacity for absorbing oxygen.
Therefore saturated salt systems can't be as corrosive as some other water-based systems.
Sodium sulfite additions (oxygen scavenger) should be, however, initiated immediately after salt
saturating the system. A residual sulfite concentration of 200 mg/l should be maintained in the
fluid at all times. High concentrations of salt tend to foam when agitated. It is recommended that
discharges from hoppers, solids removal equipment, etc., should be below the level of the fluid in
the pits. This procedure will also reduce corrosion and lead to less scavenger consumption.
Generally, the best defoamers for these systems are high alcohol types, that is, 2 or tri ethyl
hexanol.

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7.5.7 Calcium Systems

Calcium-based drilling fluids gained widespread use in the Gulf Coast area during the 1940's.
Although the reason for their development remains obscure, the most likely explanation is that
they exhibited excellent tolerance to the anhydrite (CaSO
4
) contamination commonly encountered
in East Texas. Gypsum was used in Canada in the 1950's. Modifications and subsequent
development of products to control the system properties have led to a widespread application of
Calcium-based systems in several locations worldwide.

Today Calcium Systems are often used for their inhibitive properties. The calcium ion provides an
economical source of shale hydration inhibition, when used in conjunction with an encapsulator.
Systems used for this purpose usually employ Gypsum (CaSO
4
), are of low pH, and not
deflocculated. Calcium-Based systems are still often used to drill through evaporate formations
containing anhydrite. In this case the system is usually deflocculated, with the pH running about
10.8. Again, Gypsum is usually the source of calcium.

The primary inhibitive mechanism of these water based systems, stems from the ability of the
solvated calcium ion to exchange. This occurs with the sodium ion in montmorillonite clays and to
a lesser extent the potassium ion in illites. The calcium ion, being divalent is able to satisfy 1
charge deficiency sight on each of 2 clay platelets. In the active fluid this promotes first clay
flocculation then aggregation. This same mechanism inhibits the dispersive, hydration forces in
formation clays. Cation exchange in clays is explained in the Clay Chemistry chapter (4).

This text considers mainly gyp systems. Their use is more common than Lime systems today
because they are more temperature stable than Lime systems. (At temperatures in excess of
130C a reaction between clays, calcium and Caustic Soda can cause a simple cement to form
and the drilling fluid can actually solidify). Further, Lime systems because of their high pH are less
inhibitive than gyp systems when they are formulated with seawater. This is because the clay
inhibition effect normally realized from magnesium supplied by the seawater is lost when
magnesium is precipitated as magnesium hydroxide, Mg(OH)
2
starting at about pH 10. A Lime-
based system using potassium hydroxide rather than sodium hydroxide is still in use. These
systems can work well. It is postulated that the calcium ion stabilizes the montmorillonite clays
and the potassium ion stabilizes illitic clays. These systems may use a polysaccharide
deflocculant derived from starch. (Lime systems may be classified as High Lime Mud - 1.75 - 5
kg/m
3
excess Lime or low Lime Mud - .3 - 1.0 kg/m
3
excess Lime).

Table 7.21 shows the formulation, concentrations and properties of a Gyp/PAC. The PAC
(PolyAnionic Cellulose) plays an important role as a fluid loss reducer, viscosifier and an
encapsulator. The encapsulation mechanism typical of several types of drilling fluid polymers is
explained in the Clay Chemistry Chapter (4).

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TABLE 7.21 GYP / PAC SYSTEM
a


ADDITIVE

PRODUCT NAME

CONCENTRATION (kg/m
3
)

Water
NaOH Caustic Soda 0.3
Polyanionic Cellulose Low Vis. Policell SL 9.0
Polyanionic Cellulose Hi Vis. Policell RG 3.0
CaSO
4
Gypsum 18.0
Barite Barite to 1 400 kg/m
3


Typical Properties:

Funnel Viscosity 56 s/l
Yield Point 3.5 Pa
Plastic Viscosity 20 mPaS
Gel Strengths 5.0 /10.0 Pa
Density 1 400 kg/m
3

pH 8.5
API Fluid Loss 5.0 ml / 30 min.
Calcium 4 500 mg/l
MBT as low as possible
Excess Gyp 6 kg/m
3

a
This formulation represents an initial make-up, not a conversion.


Gyp/PAC systems are usually built as opposed to converted. The formulation of this system
begins with the addition of a Biocide and Caustic Soda to the water. The Biocide suppresses
sulfate reduction and H
2
S production at the lower pH valves used. The low-viscosity PAC is
added next, followed by the high viscosity PAC to the desired yield point. The Gypsum is blended
into the system next followed lastly by the Barite.

Properties are maintained fairly easily by blending in batches of premixed chemicals. The pH of
the active system is usually maintained at 8.0 - 8.5 if adjustments to specific properties are
required they are usually made to the premix batches prior to blending premix into the active
system.

When Gyp Systems are used to drill through anhydrite, an existing Gel/Chemical system is
usually converted into a gyp System, or allowed to convert "naturally" to a Gyp System. The best
rheological stability is attained when the calcium concentration has passed the saturation point.
Sometimes a "viscosity hump" occurs as the calcium concentration increases. A reduction in
viscosity and fairly stable rheology occurs after saturation. This phenomenon is caused as the
clays in the system change from a flocculated to an aggregated state. Gypsum solubility, as well
as the corresponding calcium content is a function of pH. Thus pH control is important in
maintaining the proper level of free calcium. Figure 7.1 depicts the solubility of calcium as a
function of pH. Remember, the solubility will be suppressed further if other ions are present in the
solution.


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Firure 7.1 Solubility of Calcium as a Function of pH and
Temperature
0
100
200
300
400
500
600
700
800
10 10.5 11 11.5 12 12.5 13 13.5 14
pH
C
a
l
c
i
u
m

C
o
n
c
.

m
g
/
l
70oC
50oC
20oC

Strict attention must be paid to both the pH and the viscosity when allowing a system to "gyp
over" naturally, since both the anhydrite and the Lignosulfonate reduce the pH. System
formulation and properties are similar to those outlined in Table 7.19 (Lignosulfonate Systems),
however, the pH is maintained at 10.0 - 11.0. At this pH the soluble calcium content runs
between 600 - 1 000 mg/l. The temperature limitation of most gyp treated fluids is approximately
150C although this can be extended through the use of temperature stable organic polymers.


7.5.8 KCl Systems

The effect of the potassium ion on Bentonite swelling was first studied in the mid 1950's. Potential
benefits were seen in the increased permeability of sandstone cores when they were exposed to
filtrate containing potassium. Black and Hower offered an explanation of why the inhibiting
properties of potassium were superior to Calcium Chloride or Sodium Chloride in 1968. They
postulated that potassium has a hydrated diameter, which would favor its exchange for other
cations on clay surfaces. This mechanism is discussed in chapter 4. KCl systems gained
popularity in the 1970's as a superior method of drilling both mechanically incompetent formations
such as highly dipped shales and gumbo or mud making formations. The inhibiting mechanisms
of KCl are often augmented with an encapsulating polymer. Polyacrylamide polymers are most
often used for this purpose.

A properly formulated KCl system exhibits very good rheological characteristics. An unweighted
system usually has a high YP/PV ratio, especially if clays are a component. The shear thinning
index or n value often runs at .02 - .04 (as solids concentrations increase, this value also
increases). The low n value imparts a flat velocity profile, ensures a thin fluid at the bit and better
solids control equipment efficiency. Typically the gel strengths are high, however, there are
usually "fragile", ensuring a relatively low pump pressure required to break circulation. The
system is reasonably shear stable and temperature stable to about 120C. It is compatible with
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most water-based products. Although KCl systems containing clays are flocculated, the fluid loss
may be reduced to 2 - 4 ml with polymers. At low fluid loss values, filter cakes are thin and slick.
Deflocculants are often components of these systems. Because KCl systems are flocculated,
they are reasonably tolerant to ionic contaminants such as anhydrite.

Today K
+
salt systems are used, which incorporate non-chloride anions so as to be more
environmentally friendly. There isn't really a "basic" system. In fact the K
+
ion can be added to
almost any water-based system to act as an inhibitor. Table 7.22 describes a commonly used KCl
system. This formulation is used offshore for drilling gumbo formations such as the Miocene
Oligocene and Eocene formations. In North Sea drilling the K ion is maintained at a relatively high
concentration. This is necessary because the North Sea formations contain higher concentrations
of Smectite Clays. Note that the formulation in Table 7.22 uses K
2
CO
3
and KOH rather than the
more commonly used Na
2
CO
3
and NaOH. This is because both theory and experience indicate
that clay dispersion is reduced when the sodium concentration is minimized. If the sodium
concentration is high, sodium can and will exchange with other ions in clays such as the calcium
in calcium montmorillionite making it more dispersable. The pH is also kept fairly low, to inhibit
dispersion. The effect of pH on dispersion is discussed in the Chapter 4.


TABLE 7.22 A TYPICAL OFFSHORE KCL SYSTEM


ADDITIVE


PRODUCT NAME

CONCENTRATION (kg/m
3
)

Seawater
KCl Potassium Chloride 100 - 150
K
2
CO
3
Potassium Carbonate 2 - 6
KOH Potassium Hydroxide 2 - 6
Xanthan Gum Visco XC 84 2 - 4
CMC/PAC Polymer CMC/PAC 2 - 4

Typical Properties:

Funnel Viscosity 45 - 70 s/l
Yield Point 5 - 10 Pa
Plastic Viscosity 7 - 15 mPas
pH 8.5 - 9.0
Calcium Less than 400 mg/l
K
+
50 000 - 75 000 mg/l
Cl
-
65 000 - 90 000 mg/l
Fluid Loss 10 - 12 ml


In areas where illite containing formations are mechanically incompetent, the system imparts
borehole stability characteristics at lower concentrations of potassium. K systems used in the
Rocky Mountain Regions of North America typically have 30 40 kg/m
3
of K
+
(16,000 21,000
mg/l K
+
). These systems usually use prehydrated Bentonite as the viscosifier. A natural fluid loss
of 80 - 100 ml is usually allowed until the zone of interest is reached. North American systems
typically have a higher pH, usually maintained with sodium hydroxide. This is because the make-
up water is fresh and it contains little sodium.

Further, a high pH is required to reduce the solubility of the H
2
S encountered in the Rocky
Mountain region.

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To formulate a KCl system, calculate the required volumes and concentrations first. When PHB is
used designate and completely isolate a premix tank. Treat out the hardness and adjust the
alkalinity of the water in both the active pits and the premix tank. It is important to leave enough
room in the active pits to allow the addition of PHB and KCl. Polymers should be added to the
make-up water next since the ability of some polymers to hydrate is suppressed in a saline
environment. Good shear and a moderate mixing rate promote the best efficiency and value in
polymers. If possible, the polymers should be agitated and allowed to hydrate for 6 - 8 hours
before adding the KCl. KCl may be added rapidly if the tanks have adequate jetting and agitation.
If PHB is being used it is usually added last. The net concentration of Bentonite in the active
system should be 30-45 kg/m
3
to initiate drilling.

When using PHB an alternate method of mixing the system involves adding the KCl to a light (20
- 30 kg/m
3
) Bentonite slurry. When this method is used it is imperative that a good supply of
thinners is available. A viscosity hump similar to the situation described for Salt saturated
systems will occur at a KCl concentration of about 20-30 kg/m
3
.

When circulation through the bit is initiated, moderate shear degradation will occur. This is a
result of polymer or Bentonite structure being broken mechanically. The effect is more noticeable
when PHB is a component of the system, but it isn't adverse. Shaker screen blinding is not
uncommon during the first one or two circulations. The usual procedure is to use fairly coarse
screens initially.

Monitoring and maintaining the K
+
ion concentration is the most important aspect in managing
this system. The drilling fluids program will suggest an optimum concentration of potassium for
inhibiting a given formation. This value is usually based on past experience in a given area and
on laboratory work performed on that shale. As drilling commences the potassium ion becomes
depleted and must be replenished. The rate of depletion provides an indication of how reactive
the shales are. In new areas or on exploration wells the potassium concentration may have to be
adjusted as drilling proceeds. While drilling gumbo, the appearance of soft mushy cuttings at
surface is a good indication that the potassium concentration should be increased. Other
indicators include a drilled solids increase, a CEC increase and the occurrence of tight hole or
mud rings. When necessary, the drilling fluids Engineer should attempt to recover shale samples
for laboratory analysis. Hydration inhibition testing will provide a better guideline on subsequent
wells.

Because KCl systems are flocculated they don't tolerate high solids concentrations as well as
some other water-based systems. Therefore a good solids control program should be
implemented in conjunction with the system. Equipment monitoring and efficiency analysis is
imperative if chemical treatment costs are to be minimized. One of the best means of defense
against a solids build-up in tertiary formations is to keep bit nozzle velocities as low as possible.
This minimizes the mechanically induced dispersion of drilled solids. Simply tripping through
young formations can and often does generate literally tonnes of drilled solids, especially in
deviated wells. Therefore, the solids laden bottoms up fluid should be dumped in situations where
the solids control equipment can't keep up with the penetration rate.

Although KCl systems are flocculated, the associations of clay particles and polymers in the
suspension are usually weak. That is they are easily broken mechanically. This provides the
shear thinning character typical of the system. Structure is also readily degraded with chemical
deflocculants. Thus the addition of even small amounts of an anionic polymer such as PAC to a
KCl system can cause a marked decrease in viscosity. The effect is more noticeable if the initial
YP/PV ratio is high. Deflocculants lower the YP/PV ratio (raise the n value). Therefore a reduction
in YP/PV ratio should not be interpreted as a problem due to increasing solids, unless the density
increases. A reduction in the YP/PV ratio should not be interpreted as a solids particle size
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degradation problem unless the gel strengths increase. The addition of deflocculants to KCl
systems extends both temperature limitations and their ability to be densified.

The initial and ten-minute gel strength are generally high and flat when the system is flocculated,
however, they are also fragile. This is apparent as the viscometer dial falls back quickly and to a
large degree, when the structure is broken. In a highly shear thinning fluid, flat gel strengths are
best. Flat means that the value of the 10-second gel is close to or equal to the 10-minute value.
Flat gel strengths indicate that interparticulate structure or carrying capacity is re-established
soon after the fluid has been sheared at the bit. The Rheology chapter expands on this concept in
the subsection, Thixotrophy.

KCl systems are prone to oxygen entrainment and moderate foaming. Foaming can sometimes
result from the addition of amines during the KCl prilling (conversion to granules) process. A slight
pH increase often reduces the foam. Any KCl system should be implemented in conjunction with
a good corrosion control program. The most efficient oxygen scavenger is catalyzed sodium
sulfite. The sulfite concentration should be monitored and maintained at 200 - 400 mg/l. Corrosion
coupons should be used. Most operators and contractors maintain that an acceptable corrosion
rate is 25 - 35 mpy.


7.5.9 Aluminum Sulfate Systems

In the early 1970's a patent filed by Reed proposed the use of an aluminum complex to aid in
inhibiting clay swelling in completion and waterflood applications. Milchem Incorporated of
Houston was granted a patent entitled "Process for the Inhibition of Swelling of Shale in Aqueous
Alkaline Medium" in 1974. Subsequent modifications produced a product, which was a dry blend
of an aluminum salt and a ligand acid. In 1985 a system was successfully implemented, which
employed a sodium aluminum oxide / aluminum sulfate compound. The system has been used in
both the American and Canadian sectors of the (Arctic) Beaufort Sea. Implementation of this
system has virtually eliminated the bit balling and mud ring problems characteristic of the tertiary
sequences in this area. This has resulted in cost savings (elimination of downtime) in excess of a
million dollars per well in some locations.

Although the aluminum ion is strongly cationic, the clay swelling inhibition mechanism of this
system is not attributed to cation exchange. Shale hydration inhibition tests show Al
3+
alone to be
a less effective inhibitor than K
+
. The Al
2
(SO
4
)
3
blend is added to solution along with NaOH such
that a specific OH : Al molar ratio is attained. A six sided molecule (hexamer) forms. This shape
mimics fairly closely the hexagonal structure on the basal surface of many clays. These
hexamers are not really soluble; they behave more like a colloid. The pH of the solution is a good
indication of what the molar ratio actually is. If the solvent is seawater, a certain amount of NaOH
will precipitate dissolved salts. The pH also affects the behavior of the solution. At either high or
low pH values, the solution will assume a gel-like consistency.

It is theorized that the Al(OH)
3
rings promote clay stabilization by satisfying the charges on the
clays they contact. The mechanism, which reduces cuttings stickiness, is likely due to a reduction
in the double layer and zeta potential of clay plates, when the aluminum compound is introduced.

Table 7.23 shows the concentrations and properties typical of the systems used in the Beaufort
Sea.


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TABLE 7.23 Al
2
(SO
4
)
3
SYSTEM

ADDITIVE

PRODUCT NAME

CONCENTRATION (kg/m
3
)

Premix:

Seawater
Al
2
(SO
4
)
3
Aluminum Sulfate 144
NaOH Caustic Soda 60 (to pH 7 - 8)

Active System:

Seawater
Al
2
(SO
4
)
3
Premix to Net 12-15 kg/m
3
Al
2
(SO
4
)
3

NaOH Caustic 2
Visco XC 84 Xanvis 4.5
Policell Polyanionic Cellulose 3

Typical Properties:

Funnel Viscosity 42 s/l
Yield Point 6 Pa
Plastic Viscosity 6 mPaS
pH 9.5
API Fluid Loss 8 ml


The Al
2
(SO
4
)
3
should be premixed in a clean, segregated tank. The Al
2
(SO
4
)
3
compound should
be added first, then the NaOH. Emphasis should be placed on safety when adding the Caustic. It
should be added through the grate on the tank, not through the hopper. If available a chemical
barrel is the safest way to add Caustic Soda.

The active system should be formulated in the normal manner. Chemical additions should be
added to net the concentrations given in Table 7.2.4 after the Al
2
(SO
4
)
3
premix has been added.
First the total hardness should be treated to below 150 mg/l with Soda Ash and the pH raised to 9
with Caustic. The polymers may be added next. They should be allowed to hydrate properly prior
to adding salt. (KCl is often used for freeze point depression in the Arctic).

Enough Al
2
(SO
4
)
3
premix should be added to net an active system concentration of 12 - 15 kg/m
3

of Al
2
(SO
4
)
3
.

As drilling proceeds, the Al
2
(SO
4
)
3
concentration is maintained by observing the condition of the
cuttings on the shaker. They should appear as free-flowing aglomerates. Sticky cuttings, bit
balling or mud rings are indications that the Al
2
(SO
4
)
3
concentration is being depleted or is
insufficient.

Quantitative monitoring of aluminum levels is difficult in the field. The method used in the onshore
laboratory requires extremely low pH values. At low pH values the test may measure reacted
aluminum also resulting in an unreliable indication of available aluminum.

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7.5.10 PHPA Systems

Today several varieties of the system are used in various locations throughout the world. PHPA
polymer systems are used where shale hydration inhibition is required. Usually KCl is a
component of the system.

The polyacrylamide polymer has active groups which make the polymer highly surface active,
and an effective shale encapsulator, as well as having a filming effect on metal surfaces, thereby
reducing or eliminating bit and BHA balling. The inhibition mechanism provided by the PHPA/KCl
combination is discussed in the chapter on Polymers - see encapsulation.

The PHPA system used by Ava is called the Avapolyvis System. Avapolyvis systems have all
the advantages of a shear thinning, low solids polymer drilling fluid with shale stabilizing
characteristics. Some of these advantages are listed below:

1. Sloughing shale in both hard shales and younger, soft shales are effectively
controlled by the encapsulation mechanisms. Further stabilization is obtained
partially by running the system at lower pH values - reducing the dispersion of the
formation.

2. ROP optimization is achieved by improved bit hydraulics due to lower solids
concentrations. The high lubricity of the polymer also helps in this respect -
torque and drag are reduced. Equipment is less subject to wear due to the higher
lubricity and protective polymer film on the equipment.

3. Surge, swab and circulation pressures are better controlled and help reduce loss
of circulation and stuck pipe, as well as kicks caused by swabbing during bit trips.

4. Cementing and formation evaluation are improved due to less erosion of the
wellbore.

5. Bit balling and the build-up of drilled cuttings on the bit, and BHA is reduced due
to the surface activity of the polymer creating a protective film on the metal
surfaces.

6. Improved solids control will minimize the dilution cost. Density and viscosity are
better controlled by the low content of solids.

7. Compatibility with most products makes the system flexible and adaptable and
possible to break over to other systems if desired.

8. The system is environmentally acceptable both ecologically and for the working
environment.

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7.6 AVA DRILLING FLUID SYSTEMS

7.6.1 Spud Muds

Native Clays

If the surface hole contains bentonitic clays and shales. The hole is normally spudded with fresh
water and the pH is adjusted in order to improve hydration of clays. The viscosity is adjusted as
required for proper hole cleaning.


Bentonite / Caustic Slurry

If there is a strong possibility for lost circulation and sloughing (gravel), the well is spudded with a
light Bentonite / Caustic slurry in order to provide borehole stability.

Treat out calcium contamination with Soda Ash (Sodium Carbonate)
Adjust the pH to 8.5 9 with Caustic Soda (Sodium Hydroxide 0.5 0.75 kg/m
3
)
Mix Bentonite at 3 5 minutes per sack raising the viscosity to 40 50 s/L (50 60 kg/m
3
)


Bentonite / Lime Slurry

This is an economical way to achieve higher funnel viscosities. However, not recommended
unless lost circulation is encountered.

Bentonite must first be mixed and allowed to hydrate
Lost Circulation Materials (LCM) are added, these include; Sawdust, Cellophane and other
fibrous materials
Then Lime (Calcium Hydroxide) is added to raise the viscosity (clay is flocculated)


7.6.2 Water Drilling

SAPP Water (Sodium Acid Pyrophosphate)

Used for short water sections, no longer than 600 m.

Drill out surface casing cement with water
While drilling ahead, SAPP is added down drill-pipe in order to disperse drilled solids and
prevent the formation of mud rings.
To control mud rings drilling detergent or polymer thinners may also be added.
Density is controlled with the addition of fresh water (dump and dilute).
SAPP water washes are also effective in helping remove filter cakes (disperses Gel and
drilled solids comprising the filter cake).

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Flocculated Water

Clear water drilling is most often used to drill upper hole sections. Penetration rates are increased
when drilled solids are not present. Flocculation is initiated with what is known as a primary
coagulant. A polymer flocculant is then added to settle out the drilled solids.

The primary coagulant is a calcium source (Ca
2+
) or Gypsum (CaSO
4
-2H
2
O).

Polymer flocculants normally used :

These are anionic polyacrylamides, which attach themselves to the coagulated drilled solids and
accelerate the settling process (sedimentation rate).

The sump is filled with at least 100 200 m
3
of fresh water. This volume of water is
necessary for proper settling time.
The calcium ion concentration is raised and maintained at approximately 300 400 mg/L with
Gypsum.
Polymer flocculant is then added through a chemical barrel full of water at the flowline
returns. The polymer combines with the already coagulated drilled solids and settles solids in
the sump.
If drilling a water section sumpless, the calcium ion concentration must be at 600 800 mg/L.
In addition, more flocculating polymer is required in order to facilitate the settling process with
the reduced volume.
Floc water is used for mud up by simply reducing the calcium ion to less than 60 mg/L with
Soda Ash (Sodium Carbonate). Lowering the calcium ion will allow Bentonite to properly
hydrate and build viscosity.


7.6.3 Bentonite / Chemical Muds

This is the most common mud system in use. It provides the necessary carrying capacity and
fluid loss control.

Viscosity is achieved with Sodium Montmorillonite (Bentonite / Gel).
Usually, 45 55 kg/m
3
is added to provide sufficient viscosity.
Caustic Soda is added (0.5 - 0.75 kg/m
3
) to control the pH at 8.5 9.0 for proper hydration of
the Bentonite and added polymers.
PAC materials (polyanionic cellulose) are mixed in order to lower the fluid loss and provide a
thin tight filter cake. Once the viscosity has been raised to 40 45 s/L it normally requires 1
kg/m
3
of PAC to reduce the API fluid loss to 8 10 ml.
A lower fluid loss is desirable in order to minimize water invasion into the formation. Fluid
invasion can cause formation damage and unstable bore hole conditions. A high fluid loss
results in thicker filter cakes and can cause problems with the drill-pipe sticking.


7.6.4 GYP Muds (Dispersed Muds)

If massive amounts of anhydrite (calcium sulfate) are to be drilled, the mud system is gypped-
over in order to drill the anhydrite without any further contamination effects from soluble Calcium.

Mud-up with a standard Bentonite / Chemical mud.
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Prior to the suspected formation containing anhydrite, the pH is raised to 10 10.5 with
Caustic Soda and maintained. Anhydrite is less soluble in this pH range, therefore hole
washout in minimized.
Prior to the formation containing anhydrite, the system is pretreated with thinners in order to
semi-disperse the system. Normally, Desco CF (quebracho) or Avafluid G71 (treated
lignosulfonate) is added in concentrations between 3 10 kg/m
3
depending on how massive
the anhydrite. Further contamination effects are controlled with Desco CF or Avafluid G71,
Caustic and a polymer thinner as required.


7.6.5 Inhibitive Drilling Fluid Systems

Bentonite / PHPA Mud

This fluid contains PHPA (partially hydrolyzed polyacrylamide), which provides shale
encapsulation. It protects water sensitive shales from hydrating and sloughing into the wellbore.
Water sensitive shales include the Fernie and Blackstone formations (these contain bentonitic
clays / smectite, which can readily hydrate).

Fill tanks with fresh water, be sure tanks have been cleaned.
Treat out calcium with Soda Ash and increase the pH to 8.5 9.0 with Caustic Soda.
Mix no more than 40 kg/m
3
of Bentonite and let this hydrate as long as possible in the tanks
before any more product additions.
Mix between 1.5 3 kg/m
3
of PHPA or polyacrylamide polymers into the system.
Then lower the fluid loss to 6 8 ml with approximately 1 1.5 kg/m
3
of Policell SL material
(polyanionic cellulose).
The viscosity is then maintained with Visco XC 84 at around 1 3 kg/m
3
. The Gel content is
normally kept low (MBT of 30 40 kg/m
3
).
PHPA polymer is added directly into the suction compartment while drilling ahead. Normally
in concentrations of 1 kg over 5 m new hole drilled. This polymer encapsulates shales due to
its size and prevents further hydration of shales and subsequent sloughing.
System is characterized by lower plastic viscosities and high yield points giving an excellent
hole cleaning fluid.

Table 7.25 IONIC RADIUS OF COMMON IONS IN DRILLING FLUIDS

ION Dehydrated Radius A Hydrated Radius A
Na
+
0.95 *2.75 5.6
Mg
2+
0.65 10.8
Ca
2+
0.95 9.5
K
+
1.33 *2.32 3.8
NH
4
+
1.43 similar to K
+


Where A = Angstroms or 1 x 10
-10
m. * A range is given because different techniques for
measuring the ion radius give rise to different values

The Potassium ion K
+
and Ammonium ion NH4
+
have a small ionic radius and can fit neatly into
the hexagonal holes in the silica layer and very effectively neutralize the charge deficiency in that
layer.
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Potassium Sulfate Muds

This salt is commonly used as a source of potassium (K
+
ion). The absence of the chloride ion as
in potassium chloride KCl makes this salt more environmentally acceptable. A 3% - 5%
concentration of potassium sulfate is effective in preventing the hydration of smectite clays. This
ion's size allows it to penetrate the clay layers and prevent the further intrusion of water. The
formation of a water layer which is necessary for a clay's hydration is then prevented.

When drilling through water sensitive shales, the use of potassium systems has had much
success. In order to provide further protection against swelling and subsequent sloughing,
polymers such as PHPA (partially hydrolyzed polyacrylamide) are generally added.

Potassium brines have had proven success as completion fluids. This brine can protect producing
formations from certain types of formation damage. A very small percentage of swelling clays
within an oil producing sandstone can cause severe blockage of a producing zone by blocking
pore throats and interstitial pore space. Swelling can also dislocate non-sensitive clays such as
kaolinite and illite, which can migrate and cause pore blockage. The use of an inhibitive salt will
reduce clay swelling damage and particle migration in freshwater sensitive zones.

Dump and clean mud tanks, the system should be initially free of all drilled solids. Fill with
fresh water and raise the pH to 8.5 9.0 with approximately 0.75 kg/m
3
Caustic Soda.
Mix 30 Kg/m
3
of Potassium Sulfate through mud hopper if a 3% K
+
ion concentration is
desired.
Then mix between 2 4 kg/m
3
of encapsulating polymer in order to give added inhibitive
qualities.
Next, mix 3 4 kg/m
3
of PAC (polyanionic cellulose) to give the required filtration control.
Salt systems are corrosive in nature, recommend the addition of 3 5 L/m
3
of a corrosion
inhibitor such as Incorr and 1 1.5 l/m
3
Deoxy SS as an oxygen scavenger.
In a separate premix tank, pre-hydrate approximately 80 90 kg/m
3
of Bentonite. Let this
slurry hydrate for as long as possible.
Displace the hole to the potassium sulfate water and begin raising the viscosity with the
addition of pre-hydrated Bentonite over 2 or more circulations.
The addition of chemical thinners may be required to control flocculation and subsequent
viscosity increases.
Maintain the MBT at 30 40 kg/m
3
with the addition of pre-hydrated Bentonite.
Supplement the viscosity with the addition of Visco XC 84 (Xanthan Gum).


Potassium Formate (KCOOH)

Potassium Formate is an excellent source of the potassium ion. This organic salt is also
biodegradable making it environmentally acceptable. The salt is a 72% active solution and when
diluted back to 5 % v/v gives a K
+
ion concentration of approximately 25,000 ppm. As a powerful
anti-oxidant, this product can protect viscosifiers and fluid loss polymers against thermal
degradation up to temperatures of at least 150
o
C. Common polymer additives in this system
would include Xanthan Gum, Starch and PAC materials.

With respect to formation damage, potassium formate is compatible with formation waters
containing sulphates and carbonates, thereby reducing the chances of permeability impairment
by salt precipitation. A solution of this salt in fact will dissolve scales such as calcium sulfate and
barium sulfate (dependent on concentration).

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AVAPERM

System Description

Avaperm is a chloride free, clay inhibitor that is 100% soluble in water. As a clear liquid, it is the
principal constituent in Ava / Newparks HiPerm mud system. There are two ammonium ions
associated with the HiPerm molecule making it a divalent cation source. Therefore, after
exchange the product is not leached out, as can be the case with the monovalent potassium ion.
The hydrated ionic radius of the ammonium ion allows this product to effectively inhibit water
sensitive shales.

Shale dispersion as well as core flow testing has proven this material to be more beneficial than
potassium chloride and potassium sulfate at inhibiting clay hydration. Ava / Newpark HiPerm can
actually impart a permanent permeability increase in sandstone reservoirs containing swelling
clay. (As the clay dehydrates, the void volume within the pore system increases, resulting in a
permeability increase). In testing, when fresh water is finally passed through the plug, the
permeability remains higher than the brine baseline that was initially established.

Some added benefits include; biodegradability; non-oil wetting; non-foaming; and low-toxicity.

Basic Formulation

Product Function Concentration

Avaperm Clay Stabilizer 6 - 8 l/m
3

Visco XC

Viscosity

1.5 - 2.0 kg/m
3
Caustic Soda Alkalinity 0.2 kg/ m
3

Policell Fluid Loss 1.0 - 1.5 kg/m
3

Polivis Clay Stabilizer 3.3 kg/m
3
by mass balance



Mixing

HiPerm can be added directly to the mud system either through the hopper or directly to the
active mud over an agitator.

Maintenance
Due to its unique structure, analysis of HiPerm concentrations by a direct method is possible,
however it is best conducted in the lab.

Notes
HiPerm is effective in any pH range, however increased concentration will be required above a
pH of 10.5.

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Cleanup
Avaperm is approved for all freshwater disposal operations including the strict Landspraying
While Drilling (LWD) criteria. Microtox testing of Ava / Newpark HiPerm resulted in a pass
evaluation at concentrations of 10 l/m
3
and above. A 96-h. trout LC50 occurred at a
concentration of 7.8 l/m
3
. A 120-h lettuce seed emergence test resulted in greater than 80%
emergence at 420 mg of HiPerm per kg.


Avapolyoil/DEEPDRILL
TM
INHIBITOR

The Avapolyoil/DeepDrill
TM
drilling fluid system has been used successfully in order to provide
inhibition of water sensitive shales. This drilling fluid system performs like an oil-based drilling
fluid without the associated environmental problems. Measurements of CO
2
evolution on the
drilling fluid have found this system to be readily biodegradable and thus environmentally
friendly.

Avapolyoil/DeepDrill
TM
is a blend of Methyl Glucoside and Polyglyerine. The Methyl Glucoside
component forms a semi-permeable membrane. Due to the osmotic pressure differential created,
water is actually pulled from shales. In this way hardening of shales is observed similar to that
observed with Invert emulsions. Shale swelling and subsequent instability has been eliminated.

The Avapolyoil/DeepDrill
TM
system displays excellent filtration control as compared to other
inhibitive clay-free water based fluids, without the need for bridging materials such as calcium
carbonate. This drilling fluid has given higher return permeabilities. Increased rates of
penetration, reduced torque and drag and elimination of bit balling make this fluid an attractive
alternative to other water based drilling fluid systems.


Avabiovis (Gel-Free Drilling Fluids)
System Description
Avabiovis is a cost-effective, low damage drilling fluid designed for drilling horizontal wells where
acid stimulation is planned. The system uses acid soluble polymers that can be easily broken with
acid as well as enzymes or oxidizers. Natrosol (HEC) is the primary viscosifier since it it breaks
cleanly without residuals. Visco XCD, a clarified xanthan, is added if thixotropic properties are
required. Because Visco XCD has a charge and is branched, it may be more conducive to
creating emulsions than HEC. Acid soluble sized calcium carbonates may be used as bridging
agents if required for seepage loss reduction when overbalanced drilling. There are many sizes
and grades of Calcium Carbonate available. Ava has a good deal of experience designing these
types of bridging systems to ensure efficient size distribution and concentration as well as proper
field implementation.

Basic Formulation
Product Function Concentration

Natrosol Viscosity 3.0 4.0 kg/m
Visco XCD Viscosity 0.5 1.0 kg/m
Policell SL Filtration Control 1 1.5 kg/m
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Victosal Filtration Control 8.0 - 12.0 kg/m
Caustic Soda Alkalinity 0.4 kg/ m
3



Demulsifier Emulsion Prevention as required
Bacteriacide Bacteria Control as required
Calcium Carbonate Small Grind 10.0 - 40.0 kg/m
Calcium Carbonate Large Grind 10.0 - 40.0 kg/m

Mixing
Ensure make-up water is pretreated with a biocide. It is possible to build a concentrated system
and dilute it while displacing if pit volume is limited. Displace to Avabiovis system after drilling
cement with water. Once the system is fully displaced, add Sodium Bicarbonate as required.

Add the HEC and slowly, reducing the addition rate if fisheyes are observed. Small additions of
defoamer may be required. Add Victosal at 30 min/sack, if necessary to reduce fluid loss. Add the
Sized CaCO
3
- starting with the smallest size first. Adjust the pH if necessary with Caustic Soda.
Demulsifier should be added next. Finally add Visco XCD slowly if necessary to adjust rheology
up and attain gel strength.

Maintenance
Density as required Calcium Carbonate
Yeild Point 2 - 5 Pa Initially HEC
Gel Strengths 0/10 - 2/3Pa Initially Visco XCD
pH 9 - 10 Caustic Soda
Fluid Loss 7 - 10mils/30 min Victosal
Bacteriacide as required Avacid
Particle size as required Calcium Carbonate


Notes

Recommend keeping the system in turbulence if practical.

Start with coarse mesh shaker screens. The centrifuge can be used - after running for a short
period and evaluating its benefit. Dumping and settling will constitute a large portion of
equipment work share. Mud dumped into buried tanks could be recovered after the solids have
settled.

If seepage losses occur, add larger sized carbonates to the active system starting with an
additional 5 kg/m
3
. If losses are expected to be more severe, have a pill made up consisting of
active mud with additional carbonates added.

If it appears that solids are settling on top of telemetry equipment during trips, displace the inside
pipe volume with liquid mud system constituents only (no CaCO
3
) prior to tripping. If inside pipe
volume must be weighted, then ensure gel strengths of that fluid are adequate to suspend all
solids.
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CHAPTER 8

OIL-BASED FLUIDS

8.1 Key points and summary

8.2 Oil-based systems
8.2.1 General Description
8.2.2 Advantages
8.2.3 Disadvantages

8.3 Base Oil
8.3.1 The Structure of Base Oils
8.3.2 The Structure of Hydrocarbons
8.3.3 Analytical Terms
8.3.4 Base Oil Specifications

8.4 Brine phase
8.4.1 Balanced Activity
8.4.2 Oil to Water Ratio

8.5 Emulsifiers

8.6 Viscosity control

8.7 Fluid loss control

8.8 Solids and Solids control
8.8.1 Solids in Oil-Based Systems
8.8.2 Decreasing the Mud Density
8.8.3 Solids Control

8.9 Formulation and maintenance
8.9.1 Preparation
8.9.2 Formulation
8.9.3 Properties
8.9.4 Displacement Procedures
8.9.5 Maintenance
8.9.6 Spacers for Cementing

8.10 Drilling problems and trouble shooting
8.10.1 High Viscosity
8.10.2 Fill on Trips and Connections
8.10.3 Hole Cleaning in Large Diameter, Inclined Holes
8.10.4 High Filtration
8.10.5 Emulsion Breaking
8.10.6 Water Wet Solids
8.10.7 Salt Water Flows
8.10.8 Acid Contamination
8.10.9 Differential Sticking
8.10.10 Gas Kicks
8.10.11 Cuttings Disposal
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8.10.12 Losses to the Formation


8.11 Testing oil-based fluids
8.11.1 Emulsion Stability
8.11.2 Density
8.11.3 Rheology
8.11.4 HPHT Filtration
8.11.5 Chloride Determination
8.11.6 Alkalinity Estimation
8.11.7 Calcium Chloride Estimation
8.11.8 Sodium Chloride Estimation
8.11.9 Retort Analysis
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8.1 KEY POINTS & SUMMARY

In many aspects oil-based fluid can be described as an ideal fluid because the interaction with the
formation is minimal. The main advantages of this situation are that the borehole is stable for an
extended time period and the cuttings can come to the surface solids removal equipment in such
a size range that a significant proportion can be removed. This reduces the volume of fluid that is
used.

The main feature is a continuous low viscosity oil phase. This reduces the reaction with the polar
or water wetting formations. The oil phase also contains solids such as the weighting material
and drilled solids. Again, because of the nonpolar nature of the oil, the viscosity affects of the
solids are minimal.

Surfactants are used to make the solids oil wet and, more importantly, to emulsify the brine
phase. The emulsifiers are a special group of chemicals characterized by the presence, in the
one molecule, of two contrasting groups, one with strong attractive forces for water and the other
attracting strongly to oil. To stabilize invert of emulsions an oil soluble surfactant must be used.

The brine phase contains salts to control the activity of the brine preventing it from being drawn
from the fluid into the formation. The factors affecting the activity are detailed in the text. This is
a very important factor in formulating an oil fluid. It is not just the oil that prevents the water
entering the formation but also the high salinity of the brine phase.

Viscosity control is difficult in oil-based fluids and relies on the use of surfactant treated bentonite.
The viscosity mechanism is due to water adsorbed on the clay platelets.

Fluid loss control is very well developed in oil-based fluids and relies on colloidal particles
including colloidal sized water droplets, and differences in wettability. The fluid loss control may
be so well developed that the penetration rate is seriously limited. Therefore, invert systems can
be designed to have high fluid loss characteristics.

Oil-based systems possess properties that are highly desirable and are not obtainable with water-
based systems. One of these is the very low level of reaction with the formation, combined with
minimal penetration of the fluid phase of the fluid into the formation. This leads to maximum
borehole stability over a prolonged time span. The high level of inhibition immediately leads to a
number of important operational advantages such as:

1. Gauge borehole - important for directional drilling, log interpretation, minimal
cement volumes and good cement bonds.
2. Efficient removal of drilled solids as they have not been mechanically degraded
by a hydration reactions. This eliminates the need for excessive dilution to
control drilled solids, and results in reusable fluid at the end of the well.
3. Excellent filter cake quality that minimizes both the possibility of differential
sticking and the level of formation damage in oil-bearing sandstones.
4. Oil-based fluids have friction coefficients at least 50% lower than those of a
water-based fluid treated with lubricants. This factor is crucially important when
designing a drilling program that utilizes long, high angle holes. Physical
limitations of pipe strength and rotary table mean that certain holes should only
be drilled with oil-based fluid.

No water-based fluid system has been designed that offers these advantages.

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8.2 OIL-BASED SYSTEMS

8.2.1 General Description

Invert emulsion drilling fluids, because of their chemical composition, offer many advantages over
water-based fluids. Invert fluids have a continuous phase which is usually either diesel oil or a
low toxicity oil (for environmentally sensitive areas) and an aqueous interior phase. The interior
water phase is normally a brine solution, formulated with either calcium chloride (CaCl
2
) or
sodium chloride (NaCl). Typically, the brine is emulsified into the oil in droplets less than a
micron in diameter. Brine may constitute from 10-40% of the invert emulsion.

Invert emulsion drilling fluids are generally used where drilling problems not easily handled by
water-based fluids are expected, or in situations where the invert drilling fluid is more economical.
The major advantage offered by invert fluids, is increased borehole stability.

The following list presents some of the situations where invert emulsion drilling fluids are used:

1) To drill troublesome shales.
2) To drill deep, hot holes.
3) To drill salt, anhydrite, gypsum and potash zones.
4) To drill and core pay zones.
5) To drill through hydrogen sulfide (H
2
S) and carbon dioxide (CO
2
) containing formations.
6) To decrease torque and drag when drilling directional holes.
7) As a packer fluid for corrosion control.
8) As a workover fluid.
9) To minimize the likelihood of differential sticking.

Invert drilling fluids provide excellent rheological, filtration and oil wetting characteristics which are
easily adaptable to various pressure, temperature and wellbore conditions. In addition, these
fluids are stable in the presence of high electrolyte concentrations, soluble gases and high
temperatures.

Invert emulsion drilling fluids are composed of an oil phase, brine phase and specialty additives.
Each of these three groups serves important functions in the preparation of a stable invert
emulsion (water-in-oil) and in the maintenance of required drilling fluid properties. The additives
required in an invert emulsion drilling fluid include emulsifiers, filtration control additives, lime,
organophilic clays and weighting agents.


8.2.2 Advantages

The advantages and related benefits of oil-based fluids may be summarized as follows:

A maximum level of shale hydration inhibition is realized. A properly conditioned oil mud
should have no effect on a shale formation. Therefore, gauge hole can be drilled through
water-sensitive shales. This leads to improved cement bonding and reduced cement
requirements. Improved log response and better cuttings removal are also beneficially
affected.

The non-polar environment results in consistent fluid properties, low chemical
maintenance costs, stability under high temperature conditions, minimal effects on
properties from drilled solids, good resistance to salt and gypsum contamination and
good protection to drill string against the corrosive gases H
2
S and CO
2
.
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Formulation for low fluid loss results in low torque, especially in deviated holes, minimized
differential sticking problems, and low formation damage factors in oil reservoirs.

Formulation for high fluid loss results in high rates of penetration. The low solids content
and reduction in cuttings stickiness when using oil-based fluids also improves penetration
rates.

More competent cuttings at surface increase shale shaker workshares. Oil-based fluids
have a higher drilled solids tolerance, which can reduce dilution requirements.

Due to the excellent stability and solids tolerance, oil mud can sometimes be used for
more than one well. The re-use of oil mud can actually be cheaper than using water-
based fluids in some cases.

Oil-based fluids have application on wells with high bottom hole temperatures. Oil fluids
have shown stability in wells with logged BHT's of 300C.

Low aromatic oil-based fluids result in improved rig conditions, low odor, clean handling
on the rig, minimal effects on the marine environment, low viscosity - imparting improved
rheological priories and high flash point giving extra safety.

Other advantages include: flexibility with respect to formulation and application, reduced
corrosion rates and a reduction in tubular stress fatigue.


8.2.3 Disadvantages

The disadvantages of oil-based fluids may be summarized as follows:

1) High make-up cost.
2) Environmental restrictions including: cuttings disposal and dumping restrictions.
3) Extra fire prevention precautions are necessary.
4) Reduced rates of penetration in some areas.
5) Gas intrusion can result in barite settling.
6) Compressability of base oil makes density estimations difficult.
7) Hole cleaning and cuttings suspension may be less effective.
8) Rubber materials such as hoses of BOP components may dissolve rapidly in oil-based fluids.
9) Some types of electric logs are ineffective in oil-based fluids.
10) Gas intrusions are more difficult to detect using oil-based fluids.


8.3 BASE OIL

The liquid phases of an invert fluid are oil and emulsified water. Solids are contained solely in the
oil phase. Generally, the water content does not exceed 50% by volume of the liquid phase.
Therefore the properties of the oil greatly influence the overall properties of the fluid.

The essential function of the base oil is to provide a non-polar continuous phase and thus avoid
the polar interactions between the drilling fluid and the formation (hydration) that takes place in a
water-based fluid.

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It is important when drilling with an invert emulsion that all solids, the formation and the drilling
equipment be wetted with oil only. Therefore, enough oil must be present in the system to insure
that all components are oil wet. Under normal conditions, invert emulsion drilling fluids containing
a minimum of 70% oil should insure proper oil wetting at fluid densities up to 2,200 kg/m
3
.

Some invert emulsion fluids use diesel oil as it provides stable emulsions at an economical price.
Low toxicity oils, can be used in place of diesel oil for invert emulsion drilling in environmentally
sensitive areas.


HSE issues

Recently, concern has been raised from several industry associations about the use of high-risk
base oils in drilling muds systems. Fluids with a flash point below 61
o
C (PMCC) and high
aromatic contents should be considered high risk. Care should be taken when using such base
oils to minimize any problems that might arise.

When using base oil always read the MSDS carefully, and follow the MSDS recommendations for
safe handling procedures. Always try to limit your exposure to hydrocarbon airborne mists.
Avoid skin contact and if not possible use a recommended barrier cream to keep it off your skin.
If your clothing should become soaked with hydrocarbons a change of coveralls is recommended.
You should always wear eye protection, gloves (hydrocarbon resistant), boots (hydrocarbon
resistant) and coveralls (slicker suits) when using hydrocarbon-based fluids.

Always follow safe work practices!

As a result, operating companies have started using alternative base oils with lower aromatic
contents and higher flash points. Mud systems formulated with these lower aromatic oils provide
several advantages. Besides reducing the health hazards normally associated with exposure, the
degradation of elastomers is reduced, as is liability associated with transporting and handling as
well as any disposal issues. Despite the higher cost, many operators feel there is value added in
using low aromatic hydrocarbons for drilling.


Base oil table: Properties of Available Base Oils
Properties Drillsol HT 40N IA-35 Diesel Distillate
822
Shell
SOL D80
HDF
2000
Lamium
11C
Enviro
Drill
Density at 15
o
C
- kg/m
3

839

830

828 840

884

894 808 795 802
Flashpoint
IRP (>61
o
C)
75
o
C CC) 129
o
C
(CC)
132
o
C
(OC)
53
o
C
(CC)
77
o
C
(CC)
73
o
C
(CC)
102
o
C
(OC)
60
o
C
(CC)
80
o
C
(CC)
Aniline Point
IRP (>65
o
C)
69.9
o
C 79
o
C

92
o
C 54
o
C 58
o
C 74
o
C 89
o
C 82
o
C 65
o
C
Kinematic
Viscosity
4.20 cSt.
20
o
C
3.4 cSt.
40
o
C
3.8
cSt.
40
o
C
1.6 cSt.
40
o
C
5.7 cSt.
40
o
C
1.84 cSt.
21
o
C
3.3
cSt.
40
o
C
1.7 cSt.
40
o
C
N/A cSt.
40
o
C
Pour Point -20
o
C -33
o
C

-55
o
C -34
o
C -45
o
C <-24
o
C -45
o
C
Aromatics < 12.5% <2.2%

<0.01
%
33% high 1.90% < 1%
BTEX
IRP (<0.01 wt%)
<0.02% <0.002%
TMB
IRP (<0.3 wt%)
1.4%
Microtox
(on leachate)
Fail Pass Pass Fail Pass
(charcoal)
Pass Pass
(EPS
1/RM/24
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8.3.1 The Structures of Various Base Oils

Base oils can be broken down into two categories, synthetics and hydrocarbons.

Synthetics are base oils that are synthesized from other molecules and are generally very pure
substances. Synthetics include: linear alpha olefins (C
12
, C
14
, C
16
or C
18
) made from ethylene.


C
14
alpha olefin



Isomerized (C
12
, C
14
, C
16
or C
18
) olefin again made from ethylene. The double bond is randomly
isomerized along the carbon change. This isomerization drastically affects the viscosity and the
pour point of the synthetic oil.


C
14
olefin
C
14
olefin



Esters, are typically made from the esterification of vegetable oils with alcohols.


O
O
Ester



Iso-paraffins are made from paraffic hydrocarbons by a series of reactions with hydrogen and
platinum catalysts, this also decreases the aromatic content of the base oil.


Iso-paraffin


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One of the main properties of the synthetic base oils is that they are very biodegradable and tend
not to be toxic to marine organisms. The main drawback is the price because of all the
processing required to make the molecules, the costs of these fluids tend to be quite high.


8.3.2 The Structure of Hydrocarbon Base Oils

Hydrocarbon base oils are composed of hydrocarbons (i.e. diesel C
10
-C
18
), and come from
refined crude oil feed stocks. The composition of oils is quite complex with (typically) over 200
different molecules, but the structures can be simply described in terms of three classes of
hydrocarbons.

Paraffins have a general formula C
n
H
2n-2
. They can have a linear arrangement of molecules
where each carbon is attached to two carbon atoms or branched where the carbon can be
attached to three or four carbon atoms. These structures are given in Figure 8.1a for a C-10
paraffin. Higher paraffinics can increase the viscosity and give problems with high viscosities at
low temperatures.

C
10
H
22
142.28
142.172151
C 84.42% H 15.58%
Decane


Naphthenes have a cyclic structure with the carbon atoms typically forming a six-membered ring.
There may be more than one ring fused onto another. These structures are given in Figure 8.1b.
Naphthenes are better solvents than paraffins and provide good flow properties at low
temperatures. They may be prepared by hydrogenation of aromatic hydrocarbons.

C
6
H
12
84.16
84.093900
C 85.63% H 14.37%
C
10
H
18
138.25
138.140851
C 86.88% H 13.12%


Aromatic hydrocarbons contain carbon-carbon double bonds, which have a higher level of polar
character due to the additional electrons in the bonds rather than saturated bonds in paraffins and
naphthalenes. The structure is given in Figure 8.1c. The polar character contributes to the
solvency of the oil that is well developed. Water is more soluble in aromatic hydrocarbons than in
other hydrocarbons. The greater solvency power means that the toxic and carcinogenic
properties of oils are more closely related to the aromatic fraction. Therefore, the toxicity can be
reduced by removal of aromatic hydrocarbons. This can be done by essentially two methods of
hydrogenation and solvent extraction. The aromatic fraction also gives a characteristic odor so its
removal makes the oil more pleasant to use.

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C
6
H
6
78.11
78.046950
C 92.26% H 7.74%
C
7
H
8
92.14
92.062600
C 91.25% H 8.75%
Benzene
Toluene


Complex hydrocarbons can also be present such as those shown in Figure 8.1d where there
are paraffinic side chains on napthenic or aromatic groups.


C
10
H
12
132.21
132.093900
C 90.85% H 9.15%



8.3.3 Analytical Terms

The following terms are used to describe some of the characteristics of base oils:

Flash Point - is the temperature at which oil vapors form a flammable mixture with air. Volatile,
light, products like gasoline have a flash point below 5C. A flash point of 61C or higher is
recommended.

Fire point - is the temperature at which vapors will ignite and burn steadily. This parameter is
less important than the flash point. A point of 93C or higher is usually required.

Bubble point - is the temperature at which the oil starts to boil. An oil with a low initial boiling
point (IPB) will give off more vapor at the shakers than an oil with a high boiling point. A final
boiling point (FBP) can be defined to exclude health hazardous Poly-Aromatic-Compounds
(PAH).

The aniline point of the oil is widely used as an indication of how likely the oil-based drilling fluid
will degrade specific elastomers (rubber). The standard test for the aniline point of a mineral oil is
ASTM procedure D-611. This method measures the solvency power of the test oil for the
aromatic chemical, aniline. Aniline solubility in an oil increases as the temperature of the oil
increases. The temperature of complete solubility (where a specific volume aniline dissolves in a
specific volume test oil to form a non-cloudy solution) is called the aniline point. The lower the
temperature at which complete aniline solubility occurs, the more like the oil will damage rubber
goods. Based on experience with diesel fuel, an aniline point of at least 150F is desirable to
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minimize degradation of blowout preventer elastomers, pump swabs, shaker-screen cushions,
etc.
In cold climates, the pour point of base oil is a key factor in handling characteristics of a drilling
fluid, particularly in solids separation. The specific pour point needed for base oil depends on
local climate conditions. The pour point of oil is the lowest temperature at which the material can
be freely poured. The pour point of oil is measured by cooling a sample in 5F increments. The
test container is tilted at each temperature level. The first temperature at which the tilted sample
shows no movement within 3 seconds is called the pour point.

One of the key characteristics for a mineral oil is its aromatic content. Several different
analytical methods measure the aromatic content of oil. Three of these are: the fluorescent
indicator adsorption method; an ultraviolet light method; and an infrared light method. Each
method gives repeatable results. The UV (ultraviolet) method is used for oils containing less
than 2% aromatics, and FIA (fluorescent indicator adsorption) and IR (infrared) methods are used
for oils containing more than 2% aromatics. For proper comparison of the aromatics content of
mineral oils, it is necessary that the analytical results be from the same tests.

In the fluorescent indicator adsorption method the fluid is passed through a column of silica gel
adsorbent. The aromatic compounds are separated from the other hydrocarbon compounds
according to their unique adsorption affinities for silica gel. The aromatic content is calculated
from the length of the aromatics adsorption zone in the column. The value from this method is a
total aromatic content.

In the ultraviolet light method the UV light adsorbing of the oil is measured within the wavelength
range of 260 to 275 nanometers. Based on prior instrument calibration, this is converted into an
aromatics concentration. This concentration represents the total amount of aromatic molecules in
the oil.

In the infrared light method, the adsorption of infrared light at a specific wavelength (1,630
nanometers) is measured. This method measures only the carbon in the aromatic rings and not
the total aromatics. Any side chains on the aromatic rings are not included in the concentration
calculated from the infrared method.

Users of mineral oils should know the method(s) used to determine aromatic contents, especially
when comparing various mineral oils. Table 8.1 shows the result for mineral oils tested with the
different techniques. Note that in most of these cases the aromatic content quoted from infrared
analysis is lower than that determined by FIA. Some mineral oils used in the North Sea are
tested using the infrared method, whereas mineral oils in the U.S. are typically tested with FIA or
UV methods. This difference has led to confusion in comparing the aromatic content of mineral
oils.

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TABLE 8.2: AROMATIC CONTENT OF DIFFERENT BASE OILS USING THREE TESTING TECHNIQUES
Base Oil Tested FIA UV IR
Mineral Oil A 20 - 13
B 4 - 4
C 16 - 12
D - 0,8 -
E 16 - 14
F - 0,2 -
Diesel Fuel 30 - 25


The density of the base oil is recorded to give an indication of the lowest possible mud weight for
that particular oil.

It is desirable that the viscosity of the base oil shows little variation with temperature, an
indication of such variation can be obtained from comparison of viscosities taken at 40C and
100C.


8.3.4 Base Oil Specifications

Invert drilling fluids were traditionally formulated with diesel oil as it met the requirements of
viscosity and flash point; it was readily available at the rig site and relatively inexpensive. A
typical analysis is given in Table 8.1. It shows the high and variable content of aromatic
hydrocarbons. The oil has good solvency and formed stable emulsions.

However, concern grew for the toxic properties of diesel based fluids to the rig personnel and to
the marine environment when oil contaminated cuttings were disposed of at sea. The response
was to use more highly refined oils specifically designed to oil well drilling. A range of typical
specification is also given in Table 8.1.

The wide range of properties of the oils given in Table 8.1 stems from differences in the feed
stock available to the oil companies, processing capabilities and also from the priority given to a
particular properties of the oil.

The viscous properties of base oil are important and should be determined over a wide
temperature range. The fluid may be exposed to temperatures below 5C and should not
become too viscous to pump. The pour point should not be above -10 to -15C. The properties
of the oil influence the performance of the emulsifiers and the organoclay viscosifiers. Generally
these additives perform better in oils with higher aromatic levels. Base oils are detrimental to
elastomers as they may swell and dissolve the rubber. The higher the aniline point the lower the
solvency. The refined oils tend to be less harmful than diesel oil.


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8.4 THE BRINE PHASE

8.4.1 Balanced Activity

The brine phase contributes to the rheological and filtration properties of the drilling fluid. The
inclusion of a brine or water phase in an invert emulsion ensures that desirable non-Newtonian
properties are incorporated into the drilling fluid.

An important aspect of the brine phase is referred to as "activity". The term activity, in a drilling
sense, describes the tendency for the movement of water vapor from an area of low salt
concentration to an area of high salinity. The water activity (A
w
) is measured as a fraction of the
vapor pressure of water or relative humidity.

In an invert emulsion drilling fluid the brine phase is not isolated from the formation by the oil
phase. Water vapor may pass from the brine droplet into the formation or vice-versa depending
upon the osmotic pressure differential between the brine phase and the formation. The osmotic
pressure of the formation or brine phase is a measure of the activity and salinity of the formation
and brine. The concentration of salt in the brine phase will largely determine whether water will
flow from the brine to the formation, from the formation into the brine phase or whether there will
be no net movement of water in either direction. Table 8.3 presents different activities (A
w
) for
saturated salt solutions.


TABLE 8.3: WATER ACTIVITIES (A
W
) FOR SATURATED SOLUTIONS OF VARIOUS SALTS AT 20C.

Salt Solution

Water Activity (A
W
)
1

Distilled H
2
O 1.00
KCl 0.86
NaCl 0.76
MgCl
2
0.33
CaCl
2
0.32
1. Solutions that are not in the saturated state will have higher Aw values.


The ideal practice when drilling would be to have balanced activities between the formation water
and the drilling fluid brine phase. A balanced activity would mean that no net water migration
between the formation and brine phase would occur. The desirable balanced activity condition
may not always be possible during the drilling program since formation activities can be variable.
In practice, the brine phase is often run with a lower Aw value (higher salt concentration) than
those values expected in the formation. This results in a small net movement of water vapor from
the formation into the drilling fluid. Figure 8.2 shows how the A
w
changes with depth.

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Figure 9.2 Variation of Formation Activity with Depth for a
Normally Consolidated Sediment
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0.7 0.75 0.8 0.85 0.9 0.95
A
w
D
e
p
t
h

(
m
)


To achieve a balanced activity between the invert emulsion brine phase and the formation, an
accurate activity measurement of the formation must be known. Formation activity is best taken
from consolidated pressures either calculated from density logs or from assumptions of the
density gradient.

Brine activities are most often adjusted using sodium chloride (NaCl), or calcium chloride (CaCl
2
).
When drilling through rock salt sections or where high activities are expected, sodium chloride is
the preferred brine phase component. Calcium chloride is a general-purpose brine phase for
inverts as its activity is easily adjusted to shales of varying activities.

TABLE 8.4 CALCIUM CHLORIDE BRINE DATA (SEE ENGINEERING FIELD MANUAL).

TABLE 8.5 SODIUM CHLORIDE BRINE DATA (SEE ENGINEERING FIELD MANUAL).

The formulation of an invert fluid generally requires the oil content to be greater than the water
content so an oil to water ratio (O/W) of 50/50 is probably a minimum at the present time. The
solids contained in the system must be entrained in the oil phase so the oil content of the system,
on a volume basis, should be kept constant. Therefore, the oil content should increase as density
increases.

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TABLE 8.6: VARIATION OF OIL WATER RATIO AND MUD DENSITY

MUD DENSITY RANGE

Oil / Water Ratio
SG CONVENTIONAL HIGH WATER CONTENT
1.0-1.2 50/50 50/50
1.2-1.32 65/35 50/50
1.32-1.5 70/30 55/45
1.5-1.68 75/25 60/40
1.8-1.92 80/20 65/35

An indication of the relationship between O/W ratio and density is given in Table 8.6 for
conventional fluids and those formulated with stronger surfactants. Higher levels of oil will impart
a higher level of stability to the system providing a greater resistance to brine flows and solids
invasion. Higher oil content allows the rheological properties to be adjusted to higher ratios of
yield point to plastic viscosity or lower n values. These properties may be considered more
favorable from a point of view of hole cleaning properties.

High water content fluid formulations are used to lower the cost of the fluid and also lower the
levels of oil discharged after treatment on shaker screens. These advantages are gained at
higher risks of the mud 'flipping' and higher plastic viscosities.

The colloidal sized water droplets interact with each other and contribute to the rheological
properties, particularly the plastic viscosity. Table 8.7 gives the range of properties typically
found for an invert oil mud with density of 1200 kg/m
3
.

This shows that in high oil content systems the ratio of Plastic Viscosity to Yield Point (PV / YP)
could be adjusted to be near 1/1. In systems with a high water content it is nearer to 3/1,
indicating a decrease in the shear thinning character. This may adversely influence cuttings
transport. By comparison, the 100% oil mud exhibits low plastic viscosities.

TABLE 8.7: TYPICAL RHEOLOGICAL PROPERTIES FOR A 1,200 KG/M
3
INVERT OIL MUD
WITH DIFFERENT RATIOS OF OIL/WATER
Oil/Water
Ratio
Plastic Viscosity
CP
Yield Point
lb/100 ft
2

50/50 35-45 20
70/30 20-25 20
95/5 10-15 20


8.5 EMULSIFIERS

Preparation of a stable water-in-oil emulsion is dependent upon two factors: the size of the brine
droplets and the efficiency of emulsifiers that produce and maintain the emulsion. Smaller water
or brine droplets are produced at higher rates of mixing or shear with a more stable, tighter
emulsion resulting. A tighter emulsion is generally more viscous than a less stable emulsion.
The smaller brine droplets in a tight emulsion are less likely to coalesce when they collide than
larger droplets. It is the function of the emulsifiers to isolate the brine droplets and prevent any
coalescence.
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Emulsifiers are also important in ensuring that solids in the invert emulsion are preferentially
wetted by the continuous oil phase. Without oil wetting characteristics, the solids, especially
barite would become water wet and the overall result would be poor emulsion stability.

Invert systems use a blend of emulsifiers formulated to ensure emulsion stability for any brine at a
range of brine concentrations. The primary emulsifier is an alkyl fatty acid emulsifier. Addition of
lime to the primary emulsifier converts an "inactive" emulsifier into its "active" or working form.
This activation with lime may be depicted in Figure 8.3.

OH
O
Fatty acid
Ca(OH)
2
Activated fatty acid
2
O
O
O
O
Ca


The hydrophilic portion of the active emulsifier form is intimately associated with the brine droplet
at the oil-brine interface, while the hydrophobic portion of the emulsifier is dissolved in the
continuous oil phase.

In addition to the primary emulsifier other emulsifiers called secondary emulsifiers are required to
produce a stable invert emulsion for invert drilling fluids. These emulsifiers however, do not
require the addition of lime or any other chemical for emulsifier activity to be realized. Their
structures are depicted in Figure 8.4.



The hydrophilic portion of the emulsifier has functionalities being hydroxyl (OH), amine (NH
2
) and
/ or amide (CONH
2
), which are associated with the brine phase of the emulsion. Preparation of a
stable emulsion for the low toxicity systems requires a more powerful emulsification system than
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that normally needed for diesel-based systems. This is because a number of the low toxicity oils
are inherently more difficult to emulsify due to the low aromatic content.

When formulating an invert emulsion drilling fluid it is important to have sufficient emulsifier(s)
present to be able to coat the brine phase completely. Coalescence of brine droplets and a
resultant loss of emulsion stability will occur if insufficient emulsifier is present. Figure 8.5
represents a stable brine droplet in an oil matrix in an invert system.
Brine droplet
Oil
Oil
Oil
Figure 9.5 Emulsified Brine


8.6 VISCOSITY CONTROL

The viscous properties of an invert emulsion fluids are developed by; oil, emulsified water, oil
wetted solids (weighting agents such as barite and drilled solids) and specially processed
bentonite treated with quaternary amines (organoclays). Thus the viscous properties are
determined to a significant degree by the oil/water ratio and the fluid density. The shear thinning
character and thixotropic properties is specifically developed by the organoclay. The level of
viscosifier required will be decreased by an increase in density and water content.

The major contribution to non-Newtonian rheology is derived from organoclays. These are
bentonites in which the inorganic exchangeable cations sodium, calcium and magnesium have
been displaced by quaternary amines such as dimethyl, di (hydrogenated tallow) ammonium
chloride or dimethyl, benzyl, ammonium chloride. These cationic surfactants change the wetting
character of the bentonite from being water wettable to being oil wettable.

The viscosity properties have to be developed by the dispersion of the stacks of clay platelets.
This is achieved to some extent by mechanical factors such as shear intensity, shear time, and
temperatures. Polar compounds such as the aromatic molecules in diesel oil or water also play
an important role. Adsorption of these molecules opens up the sheets and aids the dispersion
process. Water is required to create the conductive medium in which ionic bonds and other polar
interactions can develop between the clay sheets.
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The use of organoclays is thus quite complex and will depend on many factors such as those
listed below:

Shear intensity and time
Base oil characteristics
Type of organoclay -
Clay type - montmorillonite, hectorite,
Clay processing
Quaternary amine
Emulsifier type
Temperature application

These factors should be taken into account when selecting the clay and the viscosity response
should be determined for the particular formulation.

The use of oil-based systems with high yield points in deviated wells has lead to the development
of a number of polymers that assist the viscosity developed by clays. This allows oil muds to
exhibit highly shear thinning rheology. One group of polymers is described as oil soluble
polymers. These are incorporated into the clay. The other group of products is synthetic latex
products that contribute to both fluid loss control and viscosity. They are presented as an
emulsion.


8.7 FLUID LOSS CONTROL

Invert emulsion drilling fluids typically have small fluid loss values under high temperature-high
pressure test conditions. Although test conditions cannot completely model for downhole
situations, it is likely that low fluid loss values do occur downhole during the drilling program.
There are a number of reasons for the low fluid loss values. When the invert fluid contained in
the annulus contacts the formation walls there is a small initial loss of oil to the formation. The
brine phase then acts as an impermeable membrane along the formation walls to retard the
movement of oil into the formation. In addition, the oil phase of invert fluids does not readily enter
the water-wet formations due to a high interfacial tension between the oil and formation water.

In addition to the filtration control imparted by the oil and brine phases of invert emulsions, invert
systems employ supplemental fluid loss control materials. These materials are high temperature
stable and oil dispersible. Asphaltic bitumen is the most common fluid loss additive used. Amine
treated lignite may be used in the place of asphaltic bitumen.

Relaxed oil muds have been designed for fast drilling, with a HP/HT fluid loss as high as can be
tolerated. A relaxed oil mud has the same chemical composition as an ordinary oil-based fluid.
The difference being that the former fluid system is run on the borderline between functioning and
breaking down.

To relax an oil mud and increase the fluid loss, base oil, CaCl
2
brine or water need to be added to
the mud without the usual additions of emulsifiers, oil wetting agents etc. The additions of the
emulsifiers and so on would change the mud system back towards a stable system. Relaxed oil
muds require rigorous pilot testing and continual monitoring. In order to relax a conventional oil
mud, large increases in volume have to be expected due to the amount of dilution that is required.


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8.8 SOLIDS AND SOLIDS CONTROL

8.8.1 Solids in Oil-Based Systems

All materials in an invert emulsion should be kept oil wet; this is especially important for the
weighting agents since it often constitutes a large amount of the solids content of the invert. If
barite, the usual weighting agent, is allowed to become water wet, the barite will not suspend in
the invert. An invert drilling fluid containing water-wet barite will be unstable and often take on a
dull, grainy appearance.

In a manner similar to most drilling fluids, invert emulsion formulations should contain a minimum
of drilled solids. The use of solids control equipment should efficiently remove the normally non-
dispersed drilled solids contained in the invert system. Although drilled solids are normally oil-
wetted and are thus not dispersed, the solids will disrupt the invert system by attracting water
from the brine phase in an attempt to stabilize their environment in the oil phase.

The presence of drilled solids in invert systems has the same adverse effects on the rate of
penetration as in water-based systems. Their presence requires treatment with oil wetting
agents, which can be expensive. These requirements impose an upper limit on the solids content
of the oil mud at a given oil/water ratio. Hence it is very important to optimize the use of the
available solids control equipment. The primary control of drilled solids as accomplished by the
use of fine screen, high-speed shale shakers, hydrocyclones and centrifuges.


8.8.2 Solids Control

A major limiting factor regarding solids control with oil-based fluids, as opposed to water-based
fluids, is the important fact that any dumping (transfer to a storage pit) or dilution of the system
will result in unwanted volume increases which becomes logistically difficult to store offshore and
very expensive to transport ashore for disposal. It is therefore imperative to maximize the use of
solids control equipment to remove as much drilled solids as possible. Drilled solids that are not
removed by solids control equipment must be diluted.

Shale shakers remain the best line of defense for controlling drilled solids concentrations in oil-
based systems. The advent of high-speed linear motion shakers has improved solids control
efficiency - leading to reduced costs.

In an unweighted system, the desilter may be bypassed or if run, the underflow could be
screened. A mud cleaner would be used to remove sand and save fluid. A high volume
centrifuge can be used to dispose of solids. All solids should be disposed of, including barite,
until the cost of barite is greater than the cost of dilution. In weighted systems, the mud cleaner
can be run to remove sand. The centrifuge would only be run for viscosity control.

In unweighted water-based fluids, the liquid phase is the most expensive phase. As the density is
increased there is a point where the cost of the barite becomes more expensive than the liquid
phase. At this density, efforts are concentrated on barite recovery. This is not the case in oil
fluids. Hence it is necessary to try and recover both the liquid phase and the barite, yet discard
as much of the drilled solids as possible.

In a two-stage centrifuge system, the first centrifuge to recover is barite. The centrifuged fluid
would then be fed to a second (high speed) centrifuge, which would remove and discard ultra fine
solids. The "clean" fluid would then be put back into the mud system and also be used for dilution
of the first centrifuge. As long as the clean mud weight is not excessive, this procedure can be
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economical. At some point in time, whole fluid will have to be removed from the system for
viscosity control.


8.9 FORMULATIONS AND MAINTENANCE

8.9.1 Preparation

Often minor modifications to drilling rig components must be made in order to realize the
economical benefits and safety requirements of oil-based fluids. The following considerations
should be addressed:

1. All centrifugal pump lubricators should be changed from water to grease or diesel fuel to
minimize the risk of unwanted water additions.

2. All rubber components of the circulating system (BOP parts, pump parts, etc.) should be
changed to an oil resistant material such as Neoprene.

3. If a kelly cock valve is not available on the rig, one should be installed and used to
minimize lost volume on connections, etc.

4. A mud bucket should be rigged up and used regularly on trips to avoid loss of volume.

5. A lined cuttings pit or a cuttings catch tank of sufficient volume to contain the anticipated
cuttings volume will confine the cuttings in a workable manner.

6. A cuttings conveyor to move cuttings from the shaker to the cuttings holding tank or sump
is required.

7. The surface tanks should be covered and drain lines installed to ensure that rain or snow
run off does not result in unwanted water additions to the system.

8. All water lines should be secured. Cleaning on the rig, especially around the mud tanks
should be done with diesel fuel.

9. A diesel fuel wash gun should be installed at the shaker.

10. The rig floor around the rotary table should be sealed with 3" - 6" plate welded on its
edge.

11. A drain from the rotary table area should connect to a drip pan located below the rotary
table. Any spillage can be returned to the active system via another drain connected to
the flow line or a sand trap. The drainage from the floor outside the main working area
should be connected to the normal offshore drainage system.

12. A collector pan should be installed at the pipe rack with drainage to the drip pan below
the rotary table in normal circumstances and diverted to the normal rig drainage system
during heavy rain.

13. The normal rig drainage system should be modified in the areas where there is contact
with oil-based fluid. All open drains to the sea should be sealed, and diverted to a central
collecting tank for treatment/disposal. The drainage outside the general oil base contact
areas should be the normal offshore system.
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14. An outside pipe wiper should be placed below the rotary bushing to reduce spillage
during trips. Inside wipers will also reduce spillage in the racking area.

15. The drill floor rathole and mousehole must be sealed. This can be accomplished by
welding a reducer to the end of the pipe with a valve on it. Any oil mud that accumulates
in either pipe can then be drained into a drum and pumped back to the mud system or
disposed of properly.

16. All possible spill areas should be sealed off with 3" - 6" plate. This includes the mud
pump area, centrifugal pump locations, and mud hoppers. The concept is to localize and
contain all spills so that they can be soaked up with absorbents and disposed of.

17. Safeguards against oil spills should be taken. The liberal use of oil absorbent materials
and a good rig wash detergent are recommended to keep a clean rig site.

18. Adequate ventilation should be provided in the mud processing areas.


8.9.2 Formulation

Invert system formulations are usually fairly flexible enabling them to meet the required properties
for specific applications. Drilling fluid programs contain the specific concentrations of all additives
required for individual systems. When mixing a new invert system, planning is important.
Adequate tank space, materials and mixing equipment are necessary to achieve the most
economical use of system components.

1. The mixing order of chemicals is also extremely important in order to achieve a stable
system. The mixing order usually proceeds as follows:

2. Fill the mixing tank with the required volume of base oil.

3. Add total volumes of emulsifiers and fluid loss additive. Mix products thoroughly because
shear is necessary to obtain the most stable emulsion.

4. If a premix tank is available, adding the salt to the water over a 30-minute period with
agitation should premix the brine phase. Add the brine slowly to the mixing tank under
maximum shear after the diesel and chemicals have been mixed as in step 2. Premixed
brine may be stored for later use.

5. Add the lime and shear. Maximum invert stability is achieved with maximum shear and
time.

6. Add clay while circulating in increments no larger than 5.0 kg/m
3
. The product requires
1-2 circulations to yield.


8.9.3 Properties

The following list of properties outlines a general set of guidelines for running invert systems,
although a wide range of fluid properties is possible.

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Density Maintain as low as formation pressures will allow by ensuring proper
operation of solids removal equipment.

Funnel Viscosity Maintain at 35-40 s/l (room temperature) by small additions of
organoclay (0.7 kg/m
3
). Insure that viscosity measurements are
accompanied by a flow line temperature reading.

Plastic Viscosity Optimum value is 15-20 mPas and is usually maintained by
controlling solids. PV may be reduced by the addition of oil and
increased by adjusting the oil/brine ratio. An increase in fluid density
will result in higher PV's.

Yield Point 1.5-4.0 Pa initially. Raise yield point by adding organoclay. A
decrease in yield point occurs by the addition of oil.

Fluid Loss High temperature/high pressure (250
o
F, 3400 kPa) filtrate should be
less than 8-10 ml and contain no water. The HT/HP fluid loss test
may be performed at various temperatures, including wellbore
temperature.

Emulsion Stability Emulsion stability should exceed the static bottom hole temperature
or 250 (whichever is greater). Low emulsion stability may be
accompanied by water in the HT/HP filtrate. If no water is present in
the HT/HP filtrate, and low emulsion stability is observed in the invert
system, suspect highly conducting salts or solids in the invert. Some
operators require emulsion stability values of above 250.

Gel Strength The gel strength ideally should be 2/4 Pa. Higher gel strengths
indicate either a degrading emulsion (increase in water content) or
excessive solids build-up.

NOTE: All rheological data (plastic viscosity, yield point and gel
strength) and emulsion stability should be attained at a constant
temperature. Commonly, a temperature of 50
o
C (120
o
F) is used.


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8.9.4 Displacement Procedures

In order to properly displace the hole from a water-based system to an invert the following
procedures should be used:

1. Reduce the rheological properties of the water-based fluid.

2. If possible, displace prior to drilling out. Always displace on bottom.

3. Clean the surface equipment and mud pits thoroughly and reseal all gates and troughs.

4. Prepare a weighted spacer (25 kg/m
3
heavier than the active mud).

5. Add additional emulsifier / surfactant or base oil / wetter to the first 10-15 m
3
of fluid to be
pumped.

6. Oil-wet the shaker screens with a mixture of base oil and surfactant.

7. Displace to invert mud by pumping first the weighted spacer, then the treated mud,
followed by the new invert mud. Keep the pump rate constant.

8. Work the pipe while displacing.

9. Dispose of any contaminated (interface) fluid.

10. Spot-check the oil/water ratio several times over the first 2-3 circulations.

11. Reduce shaker screen sizes as soon as possible.


8.9.5 Maintenance

Oil-based fluid maintenance is much easier than with water-based fluids mainly because the
drilled solids do not build up in the mud. The properties therefore stay much more stable and
maintenance essentially requires new volumes to replace the volume of new hole and the fluid
removed with the drilled solids.

The fluid loss test is the most indicative test of changes in emulsifier level. A change in the fluid
loss and, particularly, water in the filtrate is a good indication that the emulsifier level is becoming
depleted. The treatment should be made with the range of emulsifiers normally used.

The total water content of the mud should be carefully monitored and additions of new volume
made as accurately as possible to ensure that the water activity of the brine is correct.

40-45 s/l is the desired funnel viscosity range but will be governed by Yield Point requirements.
The flowline temperature should be reported with funnel viscosity measurements. Fluid velocities
of 40-45 m/min should provide good hole cleaning, although higher velocities may be required if
hole cleaning problems are noted or suspected.

The plastic viscosity (PV) of low density invert fluid should be 8 - 12 mPas. All rheology testing
should be performed at 50
o
C (122
o
F) and the temperature should be reported on the mud report.
PV is most affected by solids concentration and oil/water ratio. The PV can be decreased by
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increasing the oil content or by dilution with low solids invert mud. If desired, lowering the oil to
brine ratio can increase the PV.

The Yield Point initially should be maintained at 4-8 Pa. The YP can be increased with additions
of organoclay at 0.7 kg/m
3
per circulation. The YP can be decreased with the addition of base oil
or with certain surfactants.

HP/HT testing should be performed at the estimated BHT +10
o
C (or 90
o
C) and at a differential
pressure of 3450 kPa (500 psi). The filtrate should contain no free water. If free water is
observed in the filtrate, the emulsion should be tightened with additional emulsifier additions.

The ES should be maintained as required and can be increased with additional surfactants.

Should an influx of water occur, or a reduction of the oil/water ratio is desired, calcium chloride
94% powder only should be mixed into the active system. If calcium chloride 77% flake is used,
it must be pre-solubilized in water prior to its addition to the active system.

Maintain the excess Lime content at 2.0 kg/m
3
. This excess is required as Lime is essential to
ensure that the emulsion will not break down due to water wet solids, water flow or brine flow.
The Lime reacts with the fatty acids in the emulsifier to form stable calcium soaps. Excess Lime
will also act as an H
2
S scavenger in invert mud should sour fluids enter the system.

Maintain the density as low as formation pressures will allow by efficient use of the available
solids removal equipment.


8.9.6 Spacers for Cementing

There are two main reasons why a spacer is needed when cementing a well, which has been
drilled with an oil-base fluid:

1. The mixing of a cement slurry and an oil-base mud usually produces a highly gelled
mass. This can cause high friction pressures with danger for lost circulation, and
channels of gelled mud remaining in the annulus after the cement is in place. In severe
cases the cement mud mixture can be unpumpable and result in a failure to displace the
mud and cement to the desired position.

Low activity oil muds (high salinity water phase) may also result in flash setting of the cement.
The spacer must therefore be compatible with both cement and mud, and shall prevent,
mixing of the two systems.

2. The oil mud leaves the hole and casing walls with a film of oil on the surface, which
results in a poor bonding of the cement. The spacer should remove this oil film, and
convert the oil-wet surface to a water-wet state and thus improve the cement bonding.

The term "flush-fluid" is used to characterize a fluid designed to wash and dilute a drilling fluid
in a well bore in preparation for the cement slurry. For an oil-base mud a spacer is usually
water solution with demulsifying agents, which thin and disperse the mud, thereby aiding in its
removal. A flush may also contain, in addition to the demulsifying agents, a fluid loss
additive. Spacer fluids are designed to separate incompatible fluids and to water-wet the
formation and pipe.

In addition to fulfilling the two main goals, a spacer must also:
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1. Exhibit good fluid loss control in order to maintain its rheological properties.

2. Suspend weighting material up to the same density as the cement slurry (usually the
spacer has a density between the mud and cement slurry).

3. Be stable at high temperature and high pressure.

4. Be reasonably easy to mix and handle in the field.

The most significant factors regarding mud removal from annular space can be summarized
as follows:

1. The casing must be centralized in the borehole. In an eccentric annulus mud may not be
removed from the narrow part.

2. Casing movement, either rotation or reciprocation, aids mud removal. Pipe motion with
scratchers improves mud displacement in areas of hole enlargement.

3. The mud should be conditioned properly, that is low PV and YP and in particular low 10-
minute gel.

4. The displacement fluids should be in turbulent flow. If it is not possible to apply velocities
causing turbulence, the spacer viscosity should be higher than the mud viscosity. At
equal displacement rates, a thin spacer fluid in turbulent flow is more effective than a
thick spacer in laminar flow.

Ava Drilling Fluids has information on several cement spacers, which are recommended for use
with oil-base fluids. According to the marketing information they should all fulfill the requirements
stated above.


8.10 DRILLING PROBLEMS AND TROUBLE SHOOTING

8.10.1 High Viscosity

High viscosity can be caused by water or solids contamination. Changes in the oil/water ratio or
the solids content are the usual indicators. Remedial measures include adding base oil,
increasing solids control efficiency and increasing density to control water flows.

8.10.2 Fill on Trips and Connections

Fill is usually an indication that the rheological properties, specifically the gel strengths, are
inadequate. This can coincide with low gel strength readings and residue in viscometer cups; it
can also be an indication of possible water wetting.

8.10.3 Hole Cleaning in Large Diameter, Inclined Holes

This problem often occurs with invert systems because they exhibit low shear rate values, which
are lower than comparable water-based fluids. The condition is evidenced when excessive time
is spent back-reaming on trips. Latex polymers have been developed which increase low shear
rheology alone. This problem can usually be reduced when enough polymer is added to increase
the 3 and 6 rpm readings to between 15 and 20.
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8.10.4 High Filtration

High filtration rates are usually caused by inadequate concentrations of emulsifiers and lime.
Often water is present in the filtrate. The usual treatment is to add primary emulsifier and lime
along with a fluid loss reducing agent.

8.10.5 Emulsion Breaking

Emulsion breaking is usually caused by an inadequate concentration of emulsifiers or a lack of
proper shear or water-wet solids. Usually the ES decreases and water is observed in the filtrate.
Oil can sometimes be observed on the surface of the pits. The system takes on a dull, grainy
appearance. Usually adding proper emulsifiers and lime along with prolonged agitation will rectify
the problem.

8.10.6 Water Wet Solids

Severe settling and a soft mushy appearance of cuttings on the shaker screens indicate that the
solids (and hole) are becoming water wet. Adding a wetting agent will eliminate the problem,
which is typical on drillouts.

8.10.7 Salt and Salt Water Flows

Salt water flows and drilling through salt may result in decreased emulsion stability. Water
wetting of solids, increased viscosity and reduced oil/water ratios are also indicators. Add
emulsifiers and lime when drilling through salt. Add oil, lime, emulsifiers and possibly barite when
a salt-water flow occurs.

8.10.8 Acid Contamination

Acid contamination is caused by an intrusion of either CO
2
or H
2
S. Decreasing alkalinity is the
best indicator. Add lime to maintain the system alkalinity. When excessive H
2
S is present, add
ZnO.

8.10.9 Differential Sticking

Differential sticking of the drill string could be a problem across under pressured, porous,
permeable zones. To minimize the risk of stuck pipe, some modifications to the mud system and
to drilling practice are suggested. Reduce the HP/HT fluid loss to less than 10 cc's prior to
penetrating zones with suspected porosity. Have small contingency stockpile of "325" and "O"
grind Calcium Carbonate bridging agent available. These products should be added to the
system if losses of whole fluid to the hole are suspected. Avoid stopping the drill collars opposite
any zone known to have high porosity and permeability.

8.10.10 Gas Kicks

Gas kicks while drilling with invert systems are often difficult to detect. This is due to the
increased solubility of gas in oil. Detection equipment and well control procedures are extremely
important when drilling with oil-based fluids.

The following gives the critical (bubble-point) pressure for gases most often encountered while
drilling with oil-based fluids.

Methane CH
4
= 4641 kPa.
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Hydrogen Sulfide H
2
S = 9008 kPa.
Carbon dioxide CO
2
= 7387 kPa.

8.10.11 Cuttings Disposal

Many different forms of cuttings removal equipment are available today. Each method has had
varying degrees of success. Oil mud cuttings can be 50 - 60% oil mud. To prevent pollution of
the surrounding environment, these cuttings can either be hauled away to a disposal site or be
processed (composted) so that they may be dumped on location, assuming environmental
controls allow the cuttings to be dumped offshore.

Many variations of a wash system have been tried. Cuttings have been sprayed or immersed into
a wash solution of water/soap. The solids removed by shale shakers, mud cleaners and
centrifuges have also been washed in the solvents. Heat systems have included a grinder/burner
combination and a fluidized bed. Retort systems have been built to evaporate the oil and water of
the cuttings, and then separate the condensed oil and water in an oil/water separator. Capacities
are usually low.

8.10.12 Losses to the Formation

A number of different materials have been used to control seepage losses while drilling with invert
fluids. Losses of invert fluid due to seepage are often controlled by addition of sized calcium
carbonate. Particle size of the calcium carbonate is of great importance so as to be able to insure
adequate formation plugging and to keep fluid loss at a minimum. The calcium carbonate should
have some particles in the barite size range in order to fill formation pores as well as some larger,
coarser particles to provide bridging properties.

Gilsonite derivatives are an alternative seepage loss material. It is non-fluorescent material with
a mean particle size in the 60-150 mesh range. When it is added to an invert fluid the particles
will swell in time to 1.5-2 times their normal size. If excessive whole fluid losses to the formation
are expected, a water-based fluid should be used.

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8.11 TESTING OIL-BASED FLUIDS

8.11.1 Emulsion Stability

EQUIPMENT: OFI STABILITY METER ESM-3013

Procedure:
1. Place the fluid in a non-conductive container and heat to 50C. (Same
temperature used in Rheology).
2. Insert probe into fluid ensuring that end is totally immersed.
3. Turn dial on meter to 10, then depress button for 10 seconds.
4. While depressing test button, turn dial slowly until the light above the dial turns
red.
5. Double the reading on the dial to determine stability of the emulsion in volts.
6. Clean probe immediately after use.

Discussion of results:

There are many variables involved in the stability of an invert emulsion, thus the emulsion stability
value should be considered with the data from a complete mud check. As a rule of thumb
however, emulsion stability should be at least 250 volts or equal to the bottom hole temperature
(whichever is greater).


8.11.2 Density

EQUIPMENT: MUD BALANCE

Procedure:

The method for obtaining the density of an invert mud is identical to that used for a water-
based fluid. Insure that the invert mud's temperature is approximately room temperature (i.e. 20-
25C) before weighing.

Conversion calculations:

kg/m
3
= Specific Gravity x 1 000
kg/m
3
= pounds/gal. x 119.826
kg/m
3
= pounds/ft
3
x 16.051


8.11.3 Rheology

EQUIPMENT: MARSH FUNNEL

The procedure for obtaining viscosity of an invert fluid and a water-based fluid are identical.

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EQUIPMENT: RHEOMETER

Procedure:

1. An invert emulsion drilling fluid is normal preheated in a non-conductive container
before shear stress values are obtained. Normally a temperature of 50C is used.

Calculations:

Plastic viscosity (PV) in milli pascals = 600 - 300

Gel strength in pascals =
3
2
for 10 s. or 10 min.

Yield Point (YP) in pascals =
300 - P.V.
2



8.11.4 HT/HP Filtration

All invert systems should be tested in the following manner for filtration loss since API - 30 minute
(100 psi) does not give accurate fluid loss values for invert drilling fluids at anticipated wellbore
temperatures and pressures.

Procedure:

1. Connect the heating jacket to 110 volts or correct voltage for unit before test is to
be made. Place a thermometer in the thermometer well. Preheat the heating
jacket to 150C (or the desired temperature). Adjust the thermostat in order to
maintain constant temperature.
2. Load the cell taking care not to fill the cell closer than 10 mm (one-half inch) from
top to allow for expansion.
3. Place the cell into the heating jacket with both top and bottom valve-stems
closed. Transfer thermometer-to-thermometer well in cell.
4. Place the pressure unit on the top valve and lock in place. Place the bottom
pressure receiver and lock in place. Apply 700 kPa (100 psi) to both pressure
units with valve stems closed. Open top valve and apply 700 kPa (100 psi) to the
fluid while heating.
5. When sample reaches 150c increase the pressure of the top pressure unit to
4 100 kPa (600 psi) and open the bottom valve to start filtration. Collect the
filtrate for 30 min. maintaining temperature 3C. If desired, record surge volume
after 2 seconds. If back pressure rose above 700 kPa (100 psi) during the test,
cautiously reduce the pressure by drawing off a portion of the filtrate. Record the
total volume.
6. The filtrate volume should be corrected to a filter area of 45.8 cm
2
. (The filter
area is 22.9 cm
2
, double filtrate volume and report.)
7. At the end of the test, close both valve stems. Back T-screw off and bleed
pressure from both regulators. CAUTION: Filter cell will still contain
approximately 3,400 kPa (500 psi). Maintain cell in upright position and cool to
room temperature before releasing cell pressure.

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8.11.5 Chloride Determination

Method 1: Silver Nitrate Titration

Procedure:

To 100 ml of a 1:1 mixture of xylene / isopropranol, add one ml of oil mud. Stir, then dilute the
mixture with 75 ml distilled water. Add ten drops of phenolphthalein indicator. Titrate with 0.1N
H
2
SO
4
until the pink color disappears. Then add one ml of potassium chromate indicator to the
mixture, and titrate the solvents/water phase with 0.1N AgNO
3
until the color changes from yellow
to brick red. Adequate ventilation should be maintained using this procedure to avoid inhalation
of the organic solvents.

Calculations:

(1) If 0.1N silver nitrate is used:
g/l Cl- = V
T
*3.545
g/l NaCl = V
T
*5.845

(2) If 1N silver nitrate is used:
g/l Cl- = V
T
*35.45
g/l NaCl = V
T
*58.45


Method 2: Mercuric Nitrate Titration

Procedure:

To 100 ml of a 1:1 mixture of xylene / isopropranol, add one ml of oil mud. Stir, then dilute with
75 ml distilled water. Acidify to pH 3 or less with 5N sulfuric acid. Add one ml of bromophenol
blue-diphenyl carbazone indicator solution, and titrate the solvent/water phase with 0.1N mercuric
nitrate to a blue-violet endpoint (stir rapidly near endpoint). Adequate ventilation should be
maintained using this procedure to avoid inhalation of the organic solvents.

Calculations: Identical to silver Nitrate Titration


8.11.6 Alkalinity Estimation

Procedure:

To 100 ml of a 1:1 mixture of xylene / isopropanol, add on ml of oil mud. Add 75 ml of distilled
water and 5 drops of phenolphthalein indicator. While rapidly stirring, titrate entire mixture with
N/10 (0.1N) H
2
SO
4
until the pink color disappears permanently.* Adequate ventilation should be
maintained using this procedure to avoid inhalation of the organic solvents.

Calculations:

Alkalinity (Mp) is number of ml of N/10 H
2
SO
4
required
Lime content in kg/m
3
= Mp x 3.69

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*Note: After pink color disappears, the determination of chloride using silver nitrate titration may
be performed on the same test solution.

8.11.7 Calcium Chloride Estimation

Procedure:

To 100 ml of a 1:1 mixture of xylene / isopropanol, add one ml of oil mud. While stirring, add 75
ml of distilled water, two ml of strong buffer and 10-15 drops of manver. While stirring rapidly,
titrate slowly the entire mixture with standard titraver to a blue-grey endpoint. Adequate
ventilation should be maintained using this procedure to avoid inhalation of the organic solvents.

Calculation:

CaCl
2
kg/m3 = 1.14 (ml of STD. titraver) - 1.5 (kg/m
3
Ca(OH)
2
)


8.11.8 Sodium Chloride Estimation

To the proceeding procedure, apply the following calculations.

Calculation:

NaCl kg/m
3
= 16.5 (ml AgNO
3
or Hg(NO
3
)
2
- 1.06 (kg/m
3
CaCl
2
)


8.11.9 Retort Analysis

EQUIPMENT: EXTERNAL HEATED MINI STILL

Procedure:

1. Fill the chamber with a freshly obtained mud sample.
2. Place the lid on the chamber allowing any excess mud to escape.
3. Remove the lid from the chamber being careful not to remove any fluid adhering
to the lid.
4. Add 5-6 drops of liquid steel wool or pack steel wool around the upper portion of
the immersion heater. The solid steel wool will give better oil/water separation.
5. Screw the lower retort chamber into the upper chamber while maintaining both
chambers in an upright position.
6. Attach the assembled retort to the condenser.
7. Add a drop of wetting agent (aerosol) to a graduated centrifuge tube and place it
under the drain of condenser. Heating is usually 20-30 minutes, depending on
fluid type.
8. Centrifuge sample if necessary to separate the oil and water layers.


CALCULATIONS: OIL/WATER RATIO

Oil/water ratio is calculated as follows:

O =
R oil
R oil + R water
X 100
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W =
R water
R oil + R water
X 100
where:
O = percent oil in liquid phase
W = percent water in liquid phase
R = retort percentage


CALCULATIONS: CORRECTED RETORT VALUES

Corrected retort values for solids and brine are calculated by using the expansion coefficient

Ex =
D water
D brine x (1 - % W/W salt)

Then,
Rc solids =
R solids
Ex

Rc brine = R water + (R solids - Rc solids)
where:
Ex = expansion coefficient of water to brine
D = density in kg/L (from Calcium Chloride brine data sheet)
%(W/W) Salt = percentage salt in brine on a weight basis. Use decimal fraction (data
obtained from Calcium Chloride brine data sheet - Table II).

Oil/brine ratio is then calculated as follows:
O =
R oil
R oil + Rc brine
X 100%

B =
Rc brine
R oil + Rc brine
X 100%

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CHAPTER 9

PRESSURE GRADIENTS, ROCK MECHANICS AND BOREHOLE STABILITY

9.1 KEY POINTS AND SUMMARY

9.2 ROCK MECHANICS AND BOREHOLE STRESSES
9.2.1 Stress Regimes in Undisturbed Rocks
9.2.2 Mechanical Properties of Rocks
9.2.3 Stresses around a Borehole
9.2.4 Mechanical Stability
9.2.5 Stress Relief with Fluid Density
9.2.6 Borehole Fracturing and Fluid Induced Stresses
9.2.7 The Stability of Inclined Boreholes

9.3 INTERACTIONS BETWEEN DRILLING FLUID AND ROCK
9.3.1 Water Adsorption
9.3.2 Inhibition Mechanisms
9.3.3 The Time Factor

9.4 ASSESSING BOREHOLE STABILITY MECHANISMS AND SEVERITY
9.4.1 Lab Testing The Physio/Chemical Relationship Between Drilling Fluid and
Rock


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9.1 KEY POINTS & SUMMARY

Drilling a hole that is stable long enough to evaluate and run casing is a major concern of our
industry. Borehole failure is directly responsible for the loss of millions of dollars each year.
Money and time are spent jarring on pipe, freepointing, washing-over, fishing, plugging-back
and side-tracking. Other consequences include excessive time spent reaming, pumping out and
doglegs resulting from poor string stabilization.

Several varieties of sedimentary rocks exist and various types of wellbore failure may occur.
These include squeezing due to overburden stresses, hydration-induced spalling, sloughing due
to bedding plane inclination or weak rock, and expansion due to pore pressure release. These
causes may be compound mechanically. If the drilling fluid column isn't dense enough,
overburden stress can force the formation rock to fail. If the fluid is too dense, its radial stress
can fracture the rock. Fluid seepage into the rock can cause chemically induced instability
problems. Fluid may be pushed into the rock via hydrostatic pressure or pulled out via osmotic or
hydration mechanisms.

An insight into the causes of borehole instability is essential for Drilling Fluid Engineers to identify
the proper steps to rectify such problems.


9.2 ROCK MECHANICS AND BOREHOLE STRESSES

9.2.1 Stress Regimes in Undisturbed Rocks


When the sediment has compacted sufficiently for grain-to-grain contact to be established, the
overburden load or stress, S, is supported by both the mineral grains and the fluid in the
remaining spaces. The relationship is expressed in equation 9.1:

S = s + P
p


Where s represents the intergranular or matrix stress and P
p
represents the pore pressure.
Normally, where the formation is freely drained and the pore spaces are interconnected, pore
pressure, P
p
is given by equation 9.2:

P
p
=
f
d

Where
f
is the pore fluid density and d is the depth. The actual gradient should be calculated by:


f
Gradient = d .00981

Where the gradient is in kPa/m and d is kg/m
3
.

The density of the pore fluid is mainly dependent on the salinity as water is essentially
incompressible. A variation in pressure gradient can result from a reduction in fluid density with
depth as the formation temperature increases. Formation pore pressure gradients are typically in
the range from 9.8 to 11.5 kPa/m.

Undisturbed rock is in a stress regime determined by the overburden stress but modified by other
factors such as rock movements and the drainage of pore fluid. Since rocks are rigidly confined
they are in equilibrium with the in situ stresses. Stresses can be considered as components
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acting in three directions at right angles to each other. The simplest case is when the three
principal stresses are equal. The vertical stress s
v
is given by the relationship, equation 9.3:

s
v
= s
v
- P
p


Often the forces are not equal and three possible arrangements can occur, as shown in Figure
9.1. s
1
is always termed the greatest principal stress, s
2
is the intermediate stress and s
3
is the
least principal stress.




Typical values for the total stress in Western Canada are given in Table 9.1.

TABLE 9.1 TYPICAL VALUES OF TOTAL STRESSES IN ELMWORTH


Location

Depth

Minimum Horizontal
Stress MPa

Maximum Horizontal
Stress MPa
69-11w6 2021 m 39.7 61.8
94 P 1 2095 m 34.5 54.0


9.2.2 Mechanical Properties of Rocks

The mechanical properties of rocks can be determined using a triaxial cell. A core is held in a
sleeve that can be pressurized to apply equal horizontal stresses. A variable load can then be
applied vertically. Measurement of the amount of deflection for a given load allows a stress-strain
curve to be developed. Figure 9.2 shows simple stress-strain curves for rocks. When looking at
these curves, remember, that stress may be related to pressure - such as the overburden
pressure.

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The stress on a rock is opposed by its matrix strength, until a yield stress value is reached.
Here the rock will yield or begin to deform. This deformation is called plastic behavior. It may
occur in soft formations until a peak strain has been reached at which point the rock will fail. In
brittle rocks the yield stress may almost equal the peak strain. Note that the deformation of rock
depends on the stress between the grains and is independent of the pore pressure. Therefore,
the effective integrannular or matrix stress is equal to the applied load or overburden, less the
pore pressure.

The peak strength is defined as the maximum stress on the curve and the peak strain is the
corresponding strain. The curves show that after failure, the rock retains some strength if it is
confined.

The strength of rock increases with confining pressure. This is because the internal friction and
hence strength has been increased as the grains are pressed closer together. Thus, there is a
trend for increased strength of rocks with depth of burial. Brittle rocks fail suddenly and are
characterized by rocks that have substantial intergranular bonding (cohesive strength) such as
sandstones, bound by silica cements, and older shales that have been extensively dewatered. In
plastic rocks the internal resistance to deformation is low. It is typified by shales with relatively
high levels of water content (15-30%) and also rock salt. Plastic rocks have a relatively higher
proportion of post peak strength than brittle rocks. Typical values of the unconfined compressive
strength of sandstone and mudstone are 30 MPa and 14 MPa respectively.


9.2.3 Stress Around a Borehole

The process of drilling a hole in stressed rock removes support and creates conditions in which
the rock is in unconfined compression. The load is transferred to a zone of "hoop" stresses that
are tangential to the sides of the wellbore. These are called the tangential stress, represented by
s
t
in Figure 9.3. The magnitude of the tangential stress is related to the magnitude of the stress
field around the hole operating at right angles to the wellbore. This is illustrated in Figure 9.3.



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When the stresses in the initial rock are all equal (s
1
=s
2
=s
3
) the magnitude of the tangential stress
will be 2s
1
. This situation is not normally encountered. The orientation of the wellbore in the
stress field is an important factor when drilling deviated holes or when drilling in tectonically
altered rocks.

If the stresses at right angles to the wellbore are not equal then the tangential stresses will not be
symmetrical and the well may tend to fail in the direction of the least stress. In this case, there is
a tendency towards oval holes or breakouts, with the short axis pointing towards the direction of
greatest stress. It is therefore, important that the direction of the hole relative to the stress regime
in the rock is understood as fully as possible. Different sedimentary rocks can behave differently
when they are penetrated if they are under one of the aforementioned stress regimes. In some
cases when problems are expected, modifying the drilling fluid program can help.


9.2.4 Mechanical Stability

This subsection looks at borehole stability in terms of the mechanical properties of the rocks
alone. The effects of drilling fluid chemistry are discussed later.

When the effective stresses acting upon the rock are less than its elastic limit, deformation is
elastic and is usually negligible, perhaps requiring minor reaming. In deep wells and close to
gauge slim holes this movement may cause problems such as pinched or stuck bits. This is
illustrated in Figure 10.4a.

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When the effective tangential stresses acting upon the rock exceed its strength the resulting
deformation is plastic, but the failed rock is still under a confining pressure, as shown in Figure
10.4b. Thus a zone of plastically deformed rock is formed around the wellbore. This failed rock
can expand into the wellbore.

The plastic deformation zone extends into the rock a sufficient distance until the borehole reaches
a point of stable equilibrium. Here the stress at the wall is reduced to the pressure exerted by the
drilling fluid. This situation is stable if the failed rock is not eroded away.



The resultant radius of the hole and the depth of this plastic failed zone depend on both the
mechanical properties of the rocks, as defined by the ductility and cohesive strength and on the
stress distribution within the plastic and elastic zones. The size of the plastic zone can be
estimated from the rock properties and the initial horizontal stresses. This may be relatively small
for brittle rocks such as sandstones and shales. Here the ratio of the outer radius of the plastic
zone can be 1.1 - 2.5 times the radius of the hole. It can be much larger for plastic formations
such as young shales and salt. The width of the plastic zone required for stability also increases
with increases in horizontal stresses. This analysis shows that the common drilling practice is to
induce mechanical stresses in the wellbore that are only partially relieved by the pressure of the
fluid in the hole. If these stresses go beyond the range of the mechanical stability of the rock,
borehole collapse will eventually occur.


9.2.5 Stress Relief with Fluid Density

The element of rock near the wellbore is subjected to large compressive forces acting on the
unconfined rock. If the hole is filled with a fluid then a radial stress s
1
r
, is exerted against the rock,
which is equal to the pressure exerted by the fluid P
h
. The effective radial stress actually only
amounts to the difference between the hydrostatic pressure and the pore fluid pressure, P
h
- P
p
.

The radial stress means that the rock is no longer unconfined, but confined triaxially. This
increases its effective strength. The radial stress also acts to reduce the tangential stress, but the
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major effect on supporting the hole is due to the added confining pressure. Thus the effective
stress at the wellbore is again given in equation 9.4:

s = S
total
-P
p


Normally, the radial stress exerted by the fluid column is sufficient to enable drilling to proceed.
Usually drilling fluid is densified to control abnormal pore pressures, however, certain borehole
stability problems require fluid density to be increased.

There are four practical applications where raising the fluid density might serve to rectify a stress
relief problem. However, the limited success rate and the prohibitive cost require close
consideration prior to adding Barite. These formations include:

1. Squeezing Tertiary Formations
2. Tight-over-Pressured, Gas Baring Shales
3. Hydratable/Sloughing Shales
4. Gas Hydrate Baring, Formations

It is drilling industry practice to place the wellbore in compression and not eliminate totally the
tangential stresses with hydrostatic pressure. This deliberately creates potentially unstable hole
conditions. The key to success is to drill a hole that is only stable for the time required to case it.
There are a number of reasons for not balancing the hoop stresses by keeping the fluid density at
minimal values.

A single factor that has a critical influence on well costs is the time taken for drilling and
completion. Time compounds the errors with each delay, contributing to increased problems.
Thus drilling rates need to be maximized - consistent with a stable borehole. The time
dependency of borehole stability problems is discussed further in this text. Raising the fluid
density can adversely affect several functions of the fluid loss characteristics. Briefly, these
include raising the chip hold down pressure, extending the limit of filtrate invasion and increasing
the potential for differential sticking. In addition the fluid rheology can be affected as barite is
added.


9.2.6 Borehole Fracturing and Fluid Induced Stresses

Fluid density can serve to effectively reduce some stability problems caused by overburden
stresses. This is accomplished by offsetting tangential stresses in the rock with radial stresses
provided by the fluid column. However, if the radial stresses become excessive, they may induce
further stability problems. Another reason for minimizing the fluid density is to keep the wellbore
in compression. This is because the tensile strength of rock is considerably less than the
compressive strength. The term tensile strength refers to the greatest longitudinal stress a
substance can bare without tearing apart. This may be up to a factor of 1:4, depending on the
rock type and the confining stresses. This is because the compressive strength comes from
frictional contact between the mineral grains and the strength of the rock is increased if the
confining pressure is increased. If the fluid column pressure exceeds the tensile strength plus
the compressive stress, fractures will be induced in a direction at right angles to the least principal
stress. In most cases the least principal stress is in the horizontal direction and so the fracture
initiates along the axis of the vertical hole, as shown in Figure 9.5.

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Breakout
S
h
S
h
S
h
S
h
Induced fracture
Figure 9.5


Drilling conditions become difficult when the stresses at right angles to the direction of the
wellbore, S
1
and S
2
in Figure 9.1 are not equal. This condition is known as stress anisotropy. If
the ratio of the stresses is in the region of 1:5 the hole assumes an oval section. At higher stress
ratios, the rock can be failing and enlarging in the direction of the least stress and may be
fractured in the direction of the greatest stress. This is illustrated in Figure 9.5 for a vertical well.

Fracturing of the rock considerably increases the risk of hole failure because the integrity of the
rock is lost. Here, the pore pressure of the fractured rock becomes equal to the drilling fluid
pressure. The drilling fluid may begin to act as a lubricant between elements of the failed rock. A
further problem is the financial and logistical consequences as considerable volumes of fluid may
be lost.

Pressure surges that induce fractures can occur when drill pipe is run into the hole too quickly.
The surge pressure depends on the configuration of the hole and drilling assembly, the rate at
which the pipe is lowered, and the rheological properties of the drilling fluid particularly the gel
strengths. The problem can occur even when running the pipe through casing because the
hydraulic stress can be conducted by the fluid towards the open hole interval.

The formation can also be fractured if the annulus is packed off by mud rings, cavings or by
drawing the pipe up into a bed of cuttings while circulating. This latter case is especially a
problem when pulling out of a deviated wellbore, particularly when circulating with top a drive.
The fluid pressure can also be increased if the cuttings are allowed to build up in the annulus.
This happens when excessive drilling rates exceed the cuttings transport ability of the drilling
fluid. The formation is often fractured when a cement slurry is pumped behind the casing since
the minimum cement density is usually around 1.8 sg which is often higher than the fracture
gradient.

In the pre-planning stage of the well, the fluid density that will fracture the well should be
calculated so that the conditions of fracture can be avoided. Most operators conduct a pressure
integrity test prior to drilling ahead in a new hole interval. This involves deliberately fracturing the
formation rock by applying pressure against it until the rock breaks. The results are used to
calculate the equivalent fluid density capable of breaking down the formation. This value is then
used as an upper limit for fluid density or shut-in casing pressure during well control procedures.

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An important consideration in hydraulic design relates to the degree of fluid-induced stresses,
which may be applied to the formation rock while circulating. These result from hydraulic
horsepower and friction loss, imparted to the hole by the drilling fluid as it travels up the annulus.
These stresses when excessive can be erosive - resulting in over gauge hole and its associated
problems. As a result, annular velocity parameters and laminar flow regimes may take precedent
over bit hydraulic parameters in softer formations. The most notable case is permafrost, where
bit nozzles are open and annular velocities are kept below 2.0 m/min; especially important when
opening 26" pilot hole to 36". The effect of annular velocity is less detrimental in deeper, more
competent formations and may not be a factor in hydraulic design. In fact, calculations on drilling
fluid shearing forces at the borehole wall show that fluid shear stresses are 5 to 6 orders of
magnitude less than borehole hoop stresses in deep holes.
1



9.2.7 The Stability of Inclined Boreholes

An important factor controlling wellbore stresses is the orientation of the principle stresses in the
formation relative to the direction of the wellbore. Normally, the largest stress acts vertically, thus
inclination of the wellbore away from the vertical brings the component of the larger stress into
play, increasing the compressive stresses. The sides of the deviated hole are also subjected to
increased mechanical stress and abrasion due to the rotation of the drill pipe.

Rocks, particularly shales, may not exhibit the same strength in all directions. Shales, for
example, are much weaker in the direction of the bedding plane or dip compared to the direction
perpendicular to the bedding plane. This is due to the plate-like structure of the clays and the
preferential orientation of their crystals. The weaker formation may lead to premature fracture
that normally wouldn't occur in a straight hole.

A further factor in inclined wells is the increase in time required for orientation and changes to the
steering assembly. Techniques such as measurement while drilling (MWD), stearable downhole
motors and Polycrystalline Diamond Compound (PDC) bits have helped to reduce the time taken
to drill directional holes. The requirement for additional support can be calculated from
knowledge of the stress field and the mechanical properties of the rocks. This often calls for
higher fluid densities than those used for a vertical well.


9.3 INTERACTIONS BETWEEN DRILLING FLUID AND ROCK

9.3.1 Water Adsorption

The previous discussion, considered the problem of borehole stability in terms of the mechanical
factors only, and ignored any influence of the drilling fluid chemistry and properties on the
mechanical properties and the stress regime of the formation rocks.

The potential for a formation to absorb water depends on the mineralogy. Water has a very
strong affinity for mineral surfaces, particularly the clay minerals. Therefore it is highest for
shales, particularly when they contain illite, montmorillonite and mixed layer clays. The
consolidation process applies pressure that forces clay surfaces closer together and displaces
the water. The work done in the consolidation process builds up a potential in the clays to adsorb
the water. Therefore the potential of the formation to adsorb water is dependent on the
consolidation history as well as the mineralogy.

Clay surfaces are charged and may retain ions of opposite charge. In the de-watering process
the water leaving the sites between layers can have a lower salinity than the water retained as
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the pore fluid. If the clays are then exposed to water having a lower salinity than the pore water
then diffusive forces can force the water into these laminar sites. This process is often referred to
as osmotic swelling. It is an important process in sodium exchanged montmorillonite but is not
significant in calcium varieties.

The adsorption of water by clays is also controlled by changes in the structure of the shale.
These may be caused by both precipitation of intergranular cement materials and by stronger
short range Van de Waals bonding forces, which play a more important role, as the clays are
forced closer to each other. Therefore, diagenetic processes and de-watering can reduce the
swelling pressure generated by the contact of water with the shales.

Older, brittle formations can often fail too, if they consist of hydratable - usually mixed layer and
illitic shales. Osmotic swelling and hydration can result in a slow decline in the tensile strength of
the rock. Water may either penetrate the bedding planes or the layers between the crystals. Any
fracture planes, perpendicular to the bedding planes may also be penetrated. The process may
require time, but eventually when the rock fails, large pieces or cavings invade the wellbore. This
failure may be almost instantaneous, resulting in stuck pipe. Cleaning cavings dictates that
special attention is paid to fluid rheology and circulation rates. The cleaning problem is
compounded if this sloughing results in an over gauge interval.

The extent of the reaction of water with the formation rock is a complex function of a number of
factors related to the composition of rocks, the pressures generated in the consolidation process,
the salinity of the pore water and the extent of diagenetic processes. These reactions may
increase the tangential stresses past the plastic limit causing the rock to fail. They may also
decrease the net strength of the rock.

The magnitude of swelling stress has been determined in laboratory studies. These have
included water adsorption data, studies on the compaction process by measuring the compaction
pressures required to de-water a sample, and by measuring the change in stresses of a sample
directly by using strain gauges. These studies have shown that stresses in the order of 7 - 70
MPa (1,000 10,000 psi) can be generated and that the type of drilling fluid used can modify their
magnitude. It is important to attempt to distinguish between hole failure due to mechanical stress
arising from hoop stresses and chemical stress arising from reaction of the formation with drilling
fluid and filtrate.


9.3.2 Inhibition Mechanisms

Fluids formulated with freshwater and high pH create conditions where clay hydration forces are
strongest. In other words, freshwater fluids have minimal inhibitive character. Here, the chemical
swelling stresses in the wellbore are very high and borehole instability is most likely to be
observed. In young sediments, the hydration stresses may be sufficient to break down the forces
holding the shale together resulting in continual failure of the wellbore. Young cuttings, also
subjected to the hydration stress, break down to colloidal sized particles in the annulus that
cannot be removed at the surface other than by dumping. The result is a badly washed out hole,
poor directional control, poor log response, high cement costs and high drilling fluid costs.

Drilling fluid chemistry or properties may be adjusted by the addition of various components to the
fluid. There are four different mechanisms whereby drilling fluid chemistry can alleviate or
minimize borehole stability:

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1. Balanced Activity (Invert Emulsion Fluids)

2. Cation Exchange (Salt Systems K
+
, Ca
2+
, Al
2
(S0
4
)
3
)

3. Encapsulation (PHPA, Amines)

4 Increase in Filtrate Viscosity (All Oil Systems)

5 Cementation of shale porosity matrix (Sodium Silicate Systems)

6. Plastering (Asphaltic Derivatives)

A wide range of drilling fluid types have been designed in an attempt to minimize the chemical
induced stress arising from water adsorption. These have been described in more detail in the
Chapters 8 + 9, on Water Based Fluids and Oil Based Fluids. Apart from raising the density and
engineering the well trajectory, there are several methods of controlling the physio-chemical
interactions between drilling fluid and rock in an effort to arrest the actual hydration and swelling
tendencies of shale. All of these methods have been studied and are well documented. They
include the following:

Balanced Activity or Vapor Exchange is discussed in SPE 2559. Fluids using this mechanism
include Invert systems and Methyl Glucoside / Deep Drill. Invert oil emulsion fluids essentially
eliminate hydration-induced stress in clays. A semi-permeable membrane (the oil phase in OBM)
must be present in order for this to occur efficiently. This membrane is permeable to water but
not to dissolved salts. It separates the water in the shale from the water in the internal phase of
the oil based mud. When salt is dissolved into the water phase of the oil based mud to lower the
activity to less than that of the shale, water vapor moves from the shale toward the brine phase.
Osmotic pressure can thus be used to offset the swelling pressure of the shale. Generally, loss
of formation water is the preferred situation as it may strengthen the shale. The changes in water
content in the fluid can be large enough to be monitored so the salinity can be adjusted as it
strives towards equilibrium.

The continuous oil phase also eliminates polar interactions between fluid and clay crystals.
(Hence when borehole stability problems are only expected to be moderate, all oil systems are
sometimes used for drilling). The lower stress levels, low filtrate invasion and high lubricity make
oil-based fluids very effective. Oil-based fluid is expensive and excessive seepage or lost
circulation problems can make its use prohibitive. There is also concern over its environmental
impact and the costs incurred to eliminate this factor. These and other factors have generated a
need for the development of water-based fluids with higher levels of inhibitive properties.

The addition of Methyl glycoside to water based mud lowers the activity of the system in a
manner similar to calcium chloride in an OBM. The Methyl Glucoside solute becomes fixed in the
near borehole surface of the shale, establishing an effective semi permeable membrane that
allows the solvent (water) to move from the shale to the mud under a chemical potential that
exceeds the hydraulic potential tending to force water into the shale. Advanced testing (SPE
27496) clearly shows that shale exposed to this system remains intact. Further, the shale is
actually harder in the vicinity of the simulated well bore that was tested.

Cation Exchange is discussed in SPE 4232. Examples of typical salts used for this purpose
include KCL or K
2
SO
4
systems. Strong or more efficient cations such as potassium or calcium
added to the drilling fluid, change out with weak cations situated between the unit layers in
swelling clays. The strong cations effectively prevent water from entering the clay lattice
slowing hydration and dispersion. This effect is significant and can be demonstrated by the fact
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that sodium bentonite does not hydrate and disperse efficiently in saltwater. This reaction
depends on the concentration of the ion, the nature of the ion and the formation minerals.
Calcium has a very high affinity for montmorillonite and may be the most efficient exchange ion.
Being multivalent, it can collapse or impede expanding sheet structures. Potassium has a high
affinity for illite and mica clays. It replaces calcium from montmorillonite and tends to reduce clay
swelling due to the lower hydration energy of the ion. Various salts are used to control the
hydration tendencies of both tertiary and older shale types.

Calcium exchange systems use Lime and Gypsum in excess to provide a reserve of calcium ions.
When Lime is added there is a potential to form a calcium silicate precipitate with free silica and
thereby strengthen the rock. The potassium ion may be added as the alkali, KOH, or more
commonly as KCl although the acetate and carbonate salts have been used where the chloride
ion presents an environmental problem. The ammonium ion has been used as an alternative to
the potassium, in areas where the potassium ion causes environmental concern. Aluminum,
(Al
2
(SO
4
)
3
), has been used successfully in tertiary formations where highly reactive clays readily
disperse in the annulus. When used in proper concentrations, the aluminum can actually cause
these particles to aggregate to a point where they are big enough to be screened out.

Laboratory studies show the exchange ion effect can reduce clay swelling significantly (in the
order of 50 - 70%), particularly with Potassium Chloride. The result depends on the salt levels
and the type of shale being studied. KCl levels of between 3 - 8% are generally effective. The
influence of salt on electrostatic repulsive forces and the ion exchange forces does reduce the
swelling stress but does not prevent water from contacting the shales. The exchange reactions
are relatively slow and the reaction rate is controlled by diffusion.

Encapsulation is discussed in SPE 10100. Examples include PHPA (partially hydrolyzed
polyacrylamide), or Amine systems. Polymer molecules are designed with their side chains
spaced apart so that they match the c-spacing on broken clay edges. The broken-edge clay
charges are pH dependant but for the most part are positive. The anionic (negative) charges on
the polymer side chains hydrogen-bond to the clay, slowing the rate of hydration and dispersion
generating a cohesive network on the mineral surface. This reduces the mobility of the water and
strengthens the rock. An important feature of the application of this concept is that the polymer
concentration should be high enough to ensure sufficient polymer is adsorbed at a level where it
is effective.

Increase in Filtrate Viscosity is discussed in SPE 2400. Examples include Pure-oil systems
and the Mixed Metal Hydroxide system (AvaMMH). If the viscosity of the base fluid or filtrate is
high, the capillary pressure required to push fluid into a shale porosity matrix is increased. If the
viscosity is great enough, the hydrostatic head will still not be high enough to exceed the capillary
pressure whereas filtrates with the viscosity of water can easily penetrate the shale matrix,
initiating hydration and swelling.

Cementation of shale porosity matrix is explained in SPE 38569. This is the inhibition
mechanism used in Sodium Silicate Systems. Silicates react with the Ca
++
and Mg
++
ions present
on chalk surfaces and in shale pore throats by gelling in the low-pH pore fluids of shales. The
precipitates / gels that are formed, plug and coat the rock near borehole wall, preventing filtrate
from entering the formation.

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Some stress relief and unconsolidation related problems can be difficult to combat with either
drilling fluid density or chemical alteration. These include:

1. Unconsolidated Gravel or Sand
2. Coal Seams
3. Permafrost
4. Gas Hydrate Bearing Formations
5. Heaving Gumbo
6. Highly Fractured Shales

In these cases, the solution could involve wiping the hole, cooling the drilling fluid, raising the
viscosity or using an asphalt derivative such as Gilsonite. These materials have proven to be
successful in inhibiting fractured formations such as the Belly River Shale found in the Western
Plains. (Fractured / sloughing formations are evidence as incessive, large-blocky cavings on the
shaker. These cavings may have white calcarious fracture lines throughout).

The topic of drilling fluid selection and design as it related to borehole stresses and other
considerations is discussed in Chapter 8, Water-Based Fluids.


9.3.3 The Time Factor

Almost any hole is potentially unstable. The stresses contributing to instability usually increase
with time. Besides inhibitive fluids systems, drilling techniques such as top drives, motors, PDC
bits and MWD systems have all aided in reducing the time taken to drill and case an interval.
Since many stability problems are time-dependant, interval lengths can increase as drilling
techniques improve. Drilling economics dictate that the time factor should never be neglected. In
many instances it may be more economical to sidetrack a problem interval than to compound the
problem by spending time cleaning and fishing.

Delayed failure may occur almost instantaneously in coal or gas hydrate formations. More
competent shales may withstand borehole stresses for longer periods - even weeks. When these
rocks finally fail, excessive amounts of cavings may be removed before the hole stabilizes, only to
have a reoccurrence at the same depth some time later. Squeezing gumbo must be wiped at
regular time intervals, sometimes several times before unimpeded bit trips can be made or casing
lowered.

With the exception of frozen hydrate and some types of rubble and coal formations, the build up
of tangential or mechanical stresses at the wellbore does not occur instantaneously. The time
factor often depends on the relationship between the level of radial stress or fluid density and the
rock characteristics. The rate of transfer of stress into the intact rock should be fast enough to
prevent the build-up of stress past the plastic failure point. The long-term mechanical strength of
the rock is lower than the short-term strength as the failure zone extends into the formation.

The hydration reactions between the drilling fluid and the formation also have time dependent
factors. A hydration reaction exhibits a time dependency due to the rate-limiting diffusion
processes of water and various ions into the rock. This process may be impeded as expansion of
the yielded rock leads to a reduction in permeability. The fluid is driven into the formation by the
same pressure that is supporting the rock (P
h
- P
p
). Fluid invasion is related to this pressure and
the altered permeability of the stressed rock. The filtrate is also pulled into the formation due to
the affinity of the rocks for water. The hydration energy depends on consolidation pressure and
mineralogy. Osmotic forces may also be significant. The rate of progress of the filtrate front
decreases with distance from the wellbore as the filtrate fans out into the formation. Hydration
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effects are essentially removed with the use of oil-based fluids. Drilling fluid with a different
temperature may generate thermal stresses in the rock, which can also be classified as a function
of time as the rock equilibrates with the new temperature conditions.


9.4 ASSESSING BOREHOLE STABILITY MECHANISMS AND SEVERITY

There are two disciplines involved when assessing borehole stability. The first is the familiar
discipline of studying the physio/chemical relationship between drilling fluid and rock. The second
has to do with rock mechanics the strength of the rock, the tectonic and overburden influences
on wellbore stability as well as other influences such as the orientation of the bedding planes
relative to the wellbore. Computer models are available to assist in predicting severity of
breakout at various wellbore diameters, inclination and mud densities. When possible, output
data is normalized by studying wells drilled in the area. The problem is that the output may be
able to tell us what density and angle are best, but may be a little fuzzy on what type of fluid to
use. Some cant even predict the benefit of using OBM. Recently, wellbore stability models have
begun to integrate physio/chemical subroutines into them.


10.4.1 Lab Testing The Physio/Chemical Relationship Between Drilling Fluid and Rock

Capillary Suction Timer Testing involves pulverizing dried cuttings and placing them in a
cylinder that sits on top of blotter paper. The fluid to be tested is poured into the cylinder and
makes its way down through the cuttings toward the paper. This fluid us usually just makeup
water and inhibitor. As the fluid seeps out the bottom of the cylinder, it closes an electric circuit,
starting the timer. As the fluid works its way out through the blotter paper, it completes a second
circuit, stopping the timer. The idea is that the longer the time, the greater the degree of
interaction between fluid and rock. With an inhibitive fluid, the time will be faster as it wont tend
to adsorb onto or absorb into the rock. The problem with the test is that a candidate fluid with a
high inherent viscosity will perform poorly as it will travel at a slower rate due to its thickness. For
example, a PHPA fluid performs poorly with this test.

In Hot Roll Dispersion Tests, cuttings are dried and screened to a minimum size, then weighed.
They are placed into the candidate solution and hot rolled at moderate temperature for 16 hours.
They are then removed, screened and dried again. After weighing, the weight loss is compared
to the other candidates. A diesel blank is also run to get an idea of the portion of weight loss
attributable to mechanical attrition with that shale. (In most of these tests it is a good idea to run
a diesel blank as well as a fresh water blank to assist with the comparison). The problem with the
test is that an inhibitor whose mechanism involves a vapor exchange or pore pressure reduction
may not work efficiently on a cutting where pore fluids and pressure and geometry are no longer
native state. For example, both diesel and PHPA may look good on this test, whereas KCl may
not.

In a Dynamic Pellet Test, cuttings are ground up into a fine powder. They are compressed into
pellets with a washer on either end, and a nail sticking up through the middle. The nail is held in
a drill press and the pellet is immersed into the candidate fluid and spun for a time. The weight
loss is then compared to that incurred with the other fluids. The problem with the test is that
reconstituted pellets are nothing at all like the shale they were made from. If you place one
bentonite pellet in a 5% KCl solution and another into a fresh water solution the pellet in the KCl
will disintegrate immediately. The pellet in the fresh water solution will get a fuzzy layer on the
outside but will remain intact. The fresh water readily hydrates the pellet outside, creating a type
of barrier. On the other hand the KCl attacks the pellet vigorously perhaps because of its high
polarity.
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In Clay Ball Tests, balls of clay are placed in test solutions. The clay ball that shows the least
weight increase after time was soaking in the most inhibitive fluid for that clay. Again, tests
conducted on cuttings may be affected by alterations in pore pressure, volume, activity. Particle
size may vary on tests where cuttings are pulverized. Its a good idea to run blanks when
possible.

The Downhole Simulation Cell (DSC) is acknowledged by industry to be the best apparatus
available for ascertaining the effects of a drilling fluid on a given shale. This equipment is set up
in the OGS Lab in Houston. A shale core is mounted in a cylinder where a sand pack surrounds
the core. It is important that the core is preserved. Preserving it insures that its fluid saturations
and hardness remain native state. The sand pack is oil saturated. Stresses are applied and
temperature is raised to simulate actual drilling conditions. A hole is drilled through the core
using the candidate fluid. As drilling commences, the pressure of the sand pack surrounding the
core is monitored. If the pressure increases, it means that the fluid is entering the core. If this
pressure decreases, it means that fluid is moving out of the rock and into the drilling fluid. When
drilling is complete, the fluid is circulated for a time. At the end of the test the degree of hole
enlargement is measured. The hardness of the rock is also measured.

This is clearly the best method of comparing the overall inhibition characteristics of each fluid. An
idea of the actual inhibition mechanism may also be gleaned from the test.
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REFERENCES

1 Woodland, David C., Borehole Instability in the Western Canadian Overthrust Belt. SPE
Drilling Engineering March 1990.


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CHAPTER 10

FLUID DESIGN

10.1 KEY POINTS AND SUMMARY

10.2 SELECTING A DRILLING FLUID

10.2.1 The First Step
10.2.2 The Second Step
10.2.3 The Third Step

10.3 PLANNING A DRILLING FLUIDS PROGRAM


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10.1 KEY POINTS AND SUMMARY

As oil wells become more difficult to drill, the problem of selecting the best drilling fluid can
become fairly complex. There are no approved criteria for drilling fluid selection. Different
operators have their own policies and processes. Often one operator will identify and
successfully use a drilling fluid system adjacent to another operator using a different system - just
as successfully. The worst case occurs when a fluid system must be replaced, or when a drilling
operation fails because an inappropriate fluid system was chosen.

Contingency planning should be a part of all drilling fluids programs. Time spent mixing
circulating or conditioning drilling fluids due to an oversight in the planning phase can be
expensive. Mixing, displacement and spotting procedures should be carefully planned in
advance to avoid lost time.

The most efficient selection of casing setting depths is often influenced by the ability to drill and
case formations with the same density and type of fluid. Often an interval has an engineering-
oriented or geology-oriented objective. A good drilling fluid will aid in meeting these objectives
and often enhance them. Engineering parameters are extended if interval lengths can be
increased, and if geological evaluation can be improved with proper fluid formulation. Thus, if the
selection of a drilling fluid system seems complicated, it is often advantageous to initially consider
each interval separately. Then a step-by-step process can be implemented in the search for the
best fluid system.


10.2 SELECTING A DRILLING FLUID

Consider using the following steps:

1. Define the objective of the interval.
2. Identify factors which may prevent rapid and economical realization of the
objective.
3. Select a drilling fluid system(s) with respect to all of the demand criteria of the
interval. (Obviously, it would be best if one system could be used throughout the
well).

10.2.1 The First Step

Defining the objective of an interval is usually the easiest. Most intervals have engineering
objectives. Various intervals are commonly called:

1. Surface Hole
2. Intermediate Hole
3. Production Hole or Slim Hole

Top hole or surface hole, may actually be up to three intervals. Offshore Arctic wells usually drill
a glory hole, conductor hole and surface hole. The engineering priority for top holes is to cement
a string of casing (pipe) in place such that while drilling successive intervals, excessive sub-
surface pressures must be directed up through it. Drilling fluid systems used to drill top hole are
often called Spud Muds.

Intermediate hole may consist of one or more intervals. The objective is to drill to the producing
formation as quickly as possible. Geological evaluation is usually conducted as drilling proceeds.
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Sometimes engineering tasks such as kicking-off or steering are also performed on intermediate
hole. Pressures and borehole stability often dictate the length of an intermediate interval.
The production hole or slim hole is the interval, which penetrates the producing formation. The
objective is geological. The goal of an exploration well is to evaluate the production potential of a
formation. With production wells, the objective is to penetrate the zone without damaging its
ability to allow fluids to flow into the wellbore. (A good exploration well often ends up being a
production well). Often engineering objectives must also be met during intermediate hole. An
example is a well drilled horizontally through a producing zone.

10.2.2 The Second Step

In drilling fluid selection involves identifying the factors, which might prevent the objective of the
interval from being met in a timely and economical manner. It is the function or functions of the
drilling fluid system to overcome these limiting factors. Some areas of concern are listed below:

1) Environmental & Safety Considerations
2) Abnormal Formation Pressures
3) High Temperatures
4) Excessive Deviation
5) Borehole Instability
6) Production Zone Damage
7) Others

Usually formation damage or high temperatures are not a problem on top hole. However, it is
possible for the other limiting factors to occur on any interval.

A primary objective of any drilling fluid research is to instill environmental and safety
considerations into system and product development. The same concerns apply when choosing
a fluid system to drill with. In some locations, certain fluid systems are not environmentally
acceptable. These might include, but are not limited to, salt systems, high pH systems or chrome
containing systems.

High temperatures, and overpressures are conditions or problems, which can be minimized or
alleviated with proper drilling fluid design. Usually the components and properties of water-based
fluids begin to become adversely affected at temperatures above 100C. Water - based systems
specially formulated to perform at high temperatures are becoming increasingly effective.
Abnormal formation pressures rule out the use of low density, low cost fluids. On high angle
wells, fluid formulation may have to be modified in order to enhance cuttings cleaning
characteristics. Low shear rate viscosities, flow regimes and lubricity characteristics may be the
most important fluid properties on these wells. The competency of the formation usually dictates
the flow regime and thus the fluid system and properties. The problem of cleaning in inclined
holes is discussed in chapter 14.

Borehole stability problems can occur on any interval. The term borehole instability usually refers
to holes becoming either bigger or smaller due to one of a number of possible causes. Some
examples are listed below:

1) Gravel and Fractured Formations
2) Evaporate Formations
3) Techtonic Squeezing
4) Overpressured Shale
5) Zones Containing Gas Hydrates
6) Permafrost
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7) High Formation Dip
8) Water Sensitive Formations

The last example, water sensitive formation presents one of the most intricate issues when
attempting to identify the potential problems in an interval. In a new field, it is important to obtain
and analyze as much data as possible from various formations, so that future drilling fluid
systems can be changed or modified appropriately. Prior to drilling offset wells, logs can provide
data on formation dip, geology, temperature and pressure / fracture gradients, and in situ water
content. While drilling, shale samples should be obtained for laboratory testing. A well-preserved
core sample is by far the best source of data. The best swelling inhibition mechanism can often
be predicted if data is analyzed properly. Analytical tests include:

1) X-Ray Diffraction
2) Cation Exchange Capacity
3) Balancing Salinity
4) Swelling Measurements
5) Dispersion Tests
6) Various Types of Stress Tests

Samples may be tested in different fluids using different inhibition mechanisms, various
concentrations of chemicals or even a combination of 2 mechanisms. (In a KCl / polymer system
the encapsulating polymer uses a physical mechanism while the potassium ion uses a chemical
inhibiting mechanism). Often a reduction in cake permeability and fluid loss is all that is required
to control problems resulting from water sensitive clays. Borehole Stability makes it clear that
hole instability is a complex problem - especially when the relationship between Drilling Fluid
chemistry and borehole stability is addressed.

The objective of main or sum hole is usually to penetrate the zone of interest for evaluation or
exploitation purposes. Proper evaluation or full production may be affected if the wellbore fluids
cause production zone damage. The following damage mechanisms can cause a decrease in
well productivity:

1) Water Block
2) Emulsion Block
3) Wettability Alteration
4) Particle Migration
5) Precipitates
6) Clay Swelling

Other common problems, which may impede achievement of the objective on any interval,
include:

1) Severe Loss Zones
2) Water Flows
3) H
2
S (also a safety consideration)
4) Bacteria
5) Differential Sticking
6 The Formation of Hydrates (safety also)
7) Torque

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10.2.3 The Third Step

Deciding on a system is a matter of assessing the available options, keeping in mind the demand
criteria of each interval and any environmental regulations. Shale analysis often points towards
one obvious choice, such as oil-based fluid. When several alternatives exist, different factors can
help narrow the choice down. The most obvious is to attempt to choose a fluid that can be used
on most or all of the intervals. Other eliminating factors are listed below:

1. Safety
- Personnel
- Environment
- Equipment

2. Logistics
- Remoteness of Location & Transportation
- Season - Weather Conditions
- Using the Least Number of Fluid Systems per Well
- Complimentary Equipment Requirements
- Testing & Lab Equipment
- Bulk-Handling Equipment
- Mixing Equipment
- Solids Control Equipment
- Storage Facilities
- Cuttings Treatment Equipment
- Filtration Equipment

3. Economics
- Availability of Base Fluid & Chemicals
- Maintenance Costs
- Buy-back Possibilities
- Disposal Problems

4. Bit Hydraulics and ROP Optimization

5. Past Experience
- Often aids in Selection, by a Process of Elimination


10.3 PLANNING A DRILLING FLUIDS PROGRAM

Formulating a drilling fluids program is usually carried out in conjunction with the Operator's
geology and engineering departments. Some Operators choose to formulate their own drilling
fluids programs. Often they request one from a service company - sometimes as part of a bid
package. The drilling fluid program should address all possible issues and propose appropriate
contingency plans. It may include:

1. Engineering Parameters
2. A Lithological Description
3. Pore Pressure Prediction
4. Casing Setting Depths
5. A Well Profile with KOP and DOP
6. Proposed Fluids System - Usually by Interval
7. Chemical Concentrations
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8. Required Fluid Properties
9. Lab Testing Results
10. Offset Well Information
11. Contingency Formulations and Procedures
- LCM Pills
- Barite Plugs
- Viscosity Sweeps
- Lubricity Pills
- Procedures and Directives from Regulatory Agencies
- Corrosion Control Program
12. A Materials and Volume Estimate by Interval
13. A solids Control Program
14. Price List

The properties of the drilling fluid of particular importance are:

1. Density - Formation Pressure Control
2. Rheology - Optimum Cleaning and Hydraulics
3. Salinity or Polymer Content
4. Alkalinity
5. Fluid Loss Characteristics


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CHAPTER 11

SOLIDS CONTROL

11.1 KEY POINTS & SUMMARY

11.2 SOLIDS AS A CONTAMINANT
11.2.1 Sources of Solids
11.2.2 Size Definition
11.2.3 Effects of Excessive Solids
11.2.4 Benefits of Solids Control

11.3 SOLIDS CONTROL EQUIPMENT
11.3.1 General Layout
11.3.2 Gumbo Box
11.3.3 Shale Shakers
11.3.4 Sand Trap and Degasser
11.3.5 Hydrocyclones
11.3.6 Mud Cleaners
11.3.7 Decanting Centrifuges

11.4 SOLIDS IN DRILLING FLUIDS
11.4.1 Unweighted Systems
11.4.2 Weighted Systems
11.4.3 Systems in Transition
11.4.4 Solids in Oil-Based Fluids

11.5 CONTROLLING SOLIDS
11.5.1 Solids Analysis
11.5.2 Particle Size Analysis
11.5.3 Dilution

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11.1 KEY POINTS AND SUMMARY

The solids in drilling fluids are either added to perform a specific function and are thus desirable
solids, or added as a contaminant and are undesirable. Desirable solids include lost circulation
material, which can generate problems due to the relatively large size. Weighting agents have a
range of densities that are higher than the drilled solids and are thus removed relatively easily by
gravity separation. Clays such as bentonite are added to exploit their colloidal properties and
perform their function better than the clays derived from shale deposits.

Undesirable solids consist of the cuttings and the fine colloidal material caused by hydration and
dispersion. The inhibitive properties of the mud as well as the type of formation are important
factors, which influence the size and shape of the cuttings that will have to be removed at the
surface. Mud circulation rate, drilling rate and hole size control the loading of cuttings in the mud.

Solids removal equipment techniques attempt to separate the various solids in the mud on the
basis of their size and density. A primary piece of solids removal equipment is the shale shaker.
These have seen significant development in both the cloth and the mode of vibration of the
screen. It is important that as large a proportion as possible of the mud solids is removed at this
stage. The sand trap is an unstirred settling tank with a rapid dump valve that protects the rest of
the system in the event that the shakers are by-passed. Hydrocyclones generate a centrifugal
force by pumping the mud into a cone where solids slide down to the bottom and the cleaned
mud exists at the top. The size of the separated solids depends on the diameter of the cone.
Mud cleaners are used in weighted muds and discharge 5-10 cm (2-4 inches) hydrocyclones onto
a fine vibrating screen. Centrifuges generate a gravitational force by rotating the mud in a bowl.
The solids are continually scraped away so the process can be continuous. They are expensive
machines to operate but offer the most control. They can be used alone to remove solids totally
or in tandem to recover weighting material and then to remove solids and recover a liquid phase.
They have particular application in the more expensive polymer based muds and oil based muds.

The solids removal equipment should be arranged so that the larger sized solids are removed
before the finer sized solids. The equipment is sized and used according to the flow rate and
type of mud that is being used. The use of solids removal equipment plays an important role in
controlling the properties and hence performance of the mud. Properly designed and operated
equipment will give better mud properties at lower costs.


11.2 SOLIDS AS A CONTAMINANT

Most people involved with drilling recognize that excessive concentrations of entrained solid
particle are the most serious and adverse form of drilling fluid contaminant. No drilling fluid
system is immune to solids contamination, and virtually all-drilling operations employ some form
of mechanical solids removal equipment.

Until the introduction of oil field decanting centrifuges in 1952, solids were removed by using
settling pits (gravity) and rudimentary (coarse) vibrating screens. 6-inch hydrocyclones were
introduced in 1954 with more efficient 4-inch cones following in 1962. In 1966 very fine, mesh
screens were introduced, with hydrocyclone/screen combinations becoming available in the early
1970's. The 1980's saw the introduction of high performance, linear motion shakers with high-
speed centrifuges also becoming commonplace.

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11.2.1 Sources of Solids

Chapter one described several ways of classifying solids in drilling fluids. Briefly they were:

1. By size; colloidal to gravel sized.
2. By surface charge; reactive or inert.
3. By how they entered the fluid; drilled solids or "commercial solids".
4. By their specific gravity; high or low gravity solids.

This chapter is primarily concerned with the third method, how they entered the fluid.
Commercial solids are sometimes called desirable solids. These materials are non-soluble
additives, which an operator pays for, to enhance a specific function of his fluid. They include:
weighting agents, clays, bridging agents, torque reducers and certain hole stabilization additives.
On the other hand, drilled solids are sometimes called undesirable solids. The source of these
solids is the formation rock, which the bit is penetrating. The term Solids Control refers to
methods by which concentrations of drilled solids are monitored and controlled.

Drilled solids are transported by the Drilling Fluid, up the annulus to be removed at the surface.
The rate at which drilled solids are generated and become entrained in the drilling fluid (their
concentration) depends on the hole size, ROP, and cuttings transport ratio.

The nature of the formation being drilled, the inhibitive nature of the Drilling Fluid, the nozzle
velocity and the flow rate influence the character of the drilled solids on their way to surface.
Character in this context refers mainly to particle size. If the formation is hard, old rock, or if the
drilling fluid is inhibitive, drilled solids particle size degradation is usually minimal. In certain
formations, using an uninhibited fluid often results in adverse particle size degradation. As
cuttings come to surface confining pressures are reduced, allowing hydration reactions to speed
up.

Soft tertiary shales in the North Sea may produce cuttings at surface where 60 - 80% of the solids
are less than 200 microns with many less than 10 microns. An invert emulsion system eliminates
the hydrational stresses causing these same cuttings to arrive at the surface essentially the same
size as they were at the bit.

Mechanical degradation occurs when nozzle velocities are excessive or when turbulent flow
regimes are being used. It also occurs in deviated wells where the cuttings are jammed between
the pipe and the low side of the hole. Mechanical degradation can also occur at surface where
drilled solids are subjected to extreme forces, inside solids removal equipment.

The size of the returning solids also depends on the relationship between the bit type and the
formation type. A PDC bit drilling through a soft formation may generate cuttings 1 cm - 2 cm
diameter whereas a diamond bit in hard shale could generate cuttings 0.1 cm or smaller. Studies
have indicated that at a given rotary RPM, drilled solids become coarser as the ROP increases.

In virtually every drilling operation, there will be solids generated at the bit, and mechanically
degraded in the circulating system, which are so small that they are beyond the point of being
captured by solids removal equipment. The goal of solids control is to keep solids in this size
range at a minimal concentration, such that dilution volumes are minimized.

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11.2.2 Size Definition

In order to effectively proceed with a discussion of small particles and how to effectively control
them in a drilling fluid environment, an appreciation of size is necessary. The universal unit for
describing small sizes in the micron () which is 1/1000 of a millimeter. Table 11.1 gives the
sizes of some common materials in microns.


TABLE 11.1 SIZES OF SOME MATERIALS AND SENSES IN MICRONS

Material/Sense

Diameter in Microns

Human Hair 30 - 200
Polen 10 - 100
Portland Cement Dust 3 - 100
Milled Flour 1 - 80
Talcum Powder 5 - 50
Red Blood Corpuscles 7.5
Human Eye Resolution, Normal 40 (min.)
Cosmetic Preparations 35 (max.)
Face and Lip Skin Sensitivity 35 (min.)
Finger Tip Sensitivity 20 (min.)
Between-Teeth Sensitivity 6 - 8 (min.)
Human Eye Resolution, Absolute 6 - 8 (min.)


The size of the solids entrained in a Drilling Fluid system range from particles measured in
millimeters down to colloidal sized particles less than a micron in diameter. Drilling Fluid solids
may be classified by size in the following manner:

Colloidal Solids <2
Silt-sized solids 2-74
Sand-sized solids above 74 or
Cuttings-sized solids any size removed by shakers

Some authorities use the term clay-sized interchangeably with colloidal-sized. This can cause
confusion because the term colloidal refers to size alone. Barite, bentonite and dolomite can all
exist in a drilling fluid as colloidal-sized solids.

11.2.3 Effects of Excessive Solids

Generally as the concentration of solid particles in a Drilling Fluid system increases, the
properties of the fluid become altered. These in turn can affect certain drilling parameters. The
effects of solids on both Drilling Fluid properties and on drilling parameters are always adverse.
They include:
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1. An increase in rheological properties (PV, YP and gel strengths)
2. An increase in filtration rate and wall thickness, compared to Bentonite.
3. An increase in the potential to become differentially stuck
4. An increase in the potential to lose circulation
5. A reduction in penetration rate
6. A decrease in bit life
7. An increase in chemical treatment requirements (cost)
8. An increase in abrasive wear on equipment

The rate or concentration of solids, which will adversely affect properties or parameters, depends
on the nature of the solids themselves. Three parameters contribute to the nature of solids in
Drilling Fluids.

1. Specific gravity
2. Reactivity (surface charge)
3. Size (net surface area per unit of weight)

If the specific gravity of solids is high, as in the case of barite (SG = 4.2) then a smaller volume
concentration and surface area is required to achieve a given density. This reduces chemical
treatment requirements and cost, since all solids adsorb both free water and commercial
chemicals.

The reactivity of the solids is also an important consideration. Solid particles retaining a high
surface charge density cause adverse rheology first. Clays are the worst offenders. The surface
charges on clay particles attract polar molecules such as water and commercial additives
including polymers, salts and sodium hydroxide. This reduces both the free water in the system
and the chemicals, which were added to purposely control certain properties. Most water-based
systems can tolerate the addition of 150 kg/m
3
of barite far more easily than 150 kg/m
3
of
bentonitic formation solids from a rheological perspective. Barite is sometimes called an "inert"
solid because its surface charge is low. Because Barite is an ionic crystal it does have broken
edge charges. These charges although small, make it necessary to add thinners to a mud
system at higher concentrations of barite.

The size of the solids entrained in a drilling fluid also dictates when mud properties and drilling
parameters will be affected. Size is directly related to surface area. Table 2.9 shows the surface
area of a 1 cm square cube as it is broken into increasingly smaller fractions. Because the
surfaces of solid particles are charged, a high surface area to weight ratio causes problems more
quickly. 120 kg/m
3
of drilled solids with a median average particle size (D
50
) of 40 microns will not
adversely affect the rheological properties of a water-based mud. If the D
50
is allowed to degrade
(mechanically or chemically) to 1.5 microns the gel strengths will become excessive.


11.2.4 The Benefits of Solids Control

The benefits of controlling the concentration and type of solids in Drilling Fluids are directly
related to cost savings and security. Cost savings include:

1. Reduced chemical requirements
2. Lower cleanup costs
3. Longer bit and equipment life
4. Improved penetration rates

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Security means:

1. Reducing the chances of becoming differentially stuck.
2. Increasing the chances of being able to break circulation after a trip, without
fracturing the formation.
3. Enhancing hole cleaning, higher YP/PV ratios and lower n values contribute to a
flatter velocity profile in the annulus.
4. Reducing the chances of losing circulation.
5. Reducing the surge and swab pressures when moving pipe.


11.3 SOLIDS CONTROL EQUIPMENT

Various prices of solids control equipment are incorporated into the surface mud system. These
are designed to remove various sized undesirable solids. Although equipment design is
continuously improved and can constitute a large capital cost, (over $200,000.00 for certain
centrifuges) nothing exists which is able to remove all of the solids in a given fluid. Further, no
equipment exists which is able to differentiate between a given barite particle and a slightly larger
drilled solid particle. Some centrifuges are able to remove particles down to the colloidal range.
Unfortunately particles are being continuously generated at the bit and degraded in the annulus
which are 1 micron and smaller. If these solids enter the Drilling Fluid at a rate faster than the
volume of new mud is being built to fill the hole, then at some point dumping and diluting will be
necessary. This point will be reached at an earlier stage if larger solids are being introduced to
the system at a rate, which exceeds the capacity of the available solids equipment. The goal of
solids control is to run and maintain the proper equipment, configured in the proper manner, as
efficiently as possible, such that the whole mud dumping and dilution is minimized.


11.3.1 General Layout

There are almost as many solids control equipment configurations as there are drilling rigs. Most
rigs have at least one inefficiency in their configuration. When designing or modeling a surface
pit system the two key points in terms of solids control are simplicity and versatility. The pieces of
equipment should be separated. That is, the overflow from one piece should discharge into the
suction compartment for the next piece of equipment downstream. Provisions should be made
for a means of backflowing if the overflow rate of any piece of equipment is greater than the
circulation rate. A versatile system is one where the desilter cone underflow can be directed
either over a screen, or to the dilution ditch (sump) or to the centrifuge suction. The centrifuge
should sit on a pit close to the suction pit, above an agitator. It should also be close to the dilution
ditch. This way it can be used for Barite recovery or solids discard without having to install
elaborate plumbing. As solids are brought to surface they should have to contend with some or
all of the following pieces of equipment in this order:

1. Gumbo Box
2. Shale Shakers
3. Sand Trap
4. Degasser
5. Desander
6. Desilter / Mud Cleaner
7. Centrifuge

Figure 11.1 depicts a general solids equipment configuration exhibiting good versatility. All pits
with the exception of the sand trap should be agitated with the proper sized agitator. Mud guns
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are a component of most pit systems. Proper agitation insures good mixing, less entrained gas
and a proper feed to the solids equipment. The mud skimmer located just prior to the suction
compartment makes it possible to maintain a static volume in the upstream tanks. This allows for
easier volume monitoring (kick detection) since the suction tank is the only one that fluctuates.


Figure 11.1 General configuration of solids control equipment


11.3.2 Gumbo Box or Chain

Most offshore rigs are equipped with a gumbo box. This is a small compartment 5-10 m
3
, located
upstream of the shale shakers. It is designed to reduce the cuttings load on the shale shakers
when mud rings, gumbo, or large chunks of formation are returning to surface. Different types of
gumbo boxes have been designed. Some like the one in figure 11.1 are similar to a sand trap,
with a large pneumatic valve on the bottom. This allows for rapid dumping. Others consist of
sloping parallel bars. The mud passes through the bars and on to the shale shakers while the
gumbo slides down the bars to the dilution ditch.


11.3.3 Shale Shakers

The mud flow from the flow line must pass over a shale shaker. A shale shaker is a vibrating
screen. There are normally two or three units acting in parallel. Some models may operate two
or more sizes of screens in series (double deck shakers). Bypass valves are present to divert the
mudflow away from the screens if required. The shale shaker is the first and therefore the most
important device for removing solids from the mud so great care should be taken in its selection,
maintenance and operation.

Screen size selection should be evaluated on the basis of the expected maximum flow rate, hole
size, penetration rate, type of mud, density of the mud and the type of formation. At shallow
depths where hole sizes are large and penetration rates rapid, the screen size may be coarser
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than is desired. The screen opening should not be the same size as the particles being
separated as this leads to rapid screen plugging. The range of mesh sizes with corresponding
size of screen opening is given in Table 11.2. Typically the minimum mesh size is 100 mesh (150
microns). Advances have been made in the design of the screens, giving longer life and rapid
screen changing capabilities.

TABLE 11.2 IADC-API Designations of representative Test Screens


Test Screen


API - IADC Designation
a


Wire Diameter Calculated
(Microns)
U.S.S. No. 50 API 50x50 (295,33.7) 213
U.S.S. No. 80 API 80x80 (177,31) 140.5
U.S.S. No. 100 API 100x100 (149,35.2) 102
TYLER No.150 API 150x150 (104,37) 65.2
U.S.S. No.200 API 200x200 (74,340) 53
U.S.S. No. 325 API 325x325 (44,31.7 34
a
The API Designation shows mesh count, opening in microns and percent open area in that order.


The volume of liquid able to pass through any screen depends on: mesh opening size, percent
open area, weave of screen, speed and amplitude of vibration, type of motion, fluid rheology,
solids content of liquid, and feed rate and type of oversized solids.

The following guidelines apply to operating shale shakers efficiently:

1. The mesh of the screen used should be the minimum size that will tolerate the
present flow rate. At least 75% of the screen should be covered with liquid mud.

2. If throughput capacity is reduced due to sticky particles reducing the open area,
increase the mesh size. Avoid using a hard jet-spray (spray bars) to aid in
initiating cuttings movement.

3. If throughput capacity is reduced due to plugging by near - aperture sized
particles, decreasing the screen size will usually help. In the case of massive
sand, oblong mesh screens are usually least apt to blind.


11.3.4 Sand Trap and Degasser

The purpose of sand traps is to provide a gravity-settling compartment for solid particles, which
have bypassed the shaker either intentionally or through a torn screen.

The drilling fluid passing through the screens should flow directly into a sand trap. A sand trap is
a small compartment (5-15 m
3
) with sloping sides and a dump valve at the bottom. The sand trap
should not be used as a suction tank for any piece of surface equipment, nor should it be
agitated. The fluid exit from the sand trap should be over a retaining weir to the next, stirred
compartment.

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A degassing unit is essential if efficient solids control efficiency is to be realized. This is because
centrifuges pumps feeding hydrocyclones lose efficiency where they are pumping gas-cut mud.
Provision for degassing equipment should be made between the sand trap and the first
hydrocyclones.


11.3.5 Hydrocyclones

A hydrocyclone develops centrifugal forces by circulating the fluid in a circular path as shown in
Figure 11.2. The fluid is pumped through centrifugal pumps to a pressure of about 40 psi,
entering the cone tangentially near the top of the cone. The spiral motion generates centrifugal
forces that throw the larger, denser particles to the outside of the cone discharging at the bottom.
Near the bottom of the cone, the clean mud reverses direction and spirals up towards the top. A
hollow cylinder, the vortex finder, extends from the top of the cone and forms the overflow outlet
for the cleaned mud. The diameter of the cone, the feed rate and pressure, the mud density and
the relative diameters of the solids discharge opening and the vortex finder are all critical
parameters that determine the performance of the hydrocyclone. The operating parameters are
summarized in Table 11.3.


TABLE 11.3 Summary of Parameters of Hydrocyclones

Hydrocyclone CMS

Diameter Inches

Feed Rate Gallons per
Minute (per cone)

Median Cut Point
30.5 12 400 100
20 8 Desander 150 50
15.25 6 100 30
10 4 Desilter 50 15-30
5 2 Desilter 25 10-25

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Figure 11.2 Hydrocyclone nomenclature

The cyclones can either be run in a "balanced" or "chokebottom" mode. The balanced design
creates a slight vacuum at the bottom discharge, drawing in air. This gives a drier discharge of
solids but there is a higher risk of blocking. A "chokebottom" mode retains a positive pressure in
the cone and a wetter discharge but the risk of blocking is minimized. The number of cones and
pump rate are ideally set at about 125% of the mud flow rate so that the cleaned mud can dilute
the incoming mud.
The following are some practical suggestions, which may be considered when operating
hydrocyclones:

1. Run hydrocyclones continuously when using unweighted mud. Use a mud
cleaner for weighted mud.

2. Use the proper cone feed pressure, and keep the cones unplugged. Using a fine
screen shale shaker or 12 inch desanders will reduce loading on 4-in. cones
operating downstream. Size both desander and desilter units to process at least
125% of the mud flow rate. Each unit should return mud to the next compartment
downstream of its suction. The suction, feed, and overflow lines should be sized
with appropriate diameters and minimum lengths, and in accordance with good
centrifugal pump installation practices.

3. Keep the cones in spray discharge. Plugging of the inlet manifold or the
individual cone inlets may cause loss of whole mud from the bottom, of the cone.
The discharge manifold should be close to atmospheric pressure; backpressure
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or a partial vacuum in this manifold will shift the cones away from their proper
balance. An easy way to maintain atmospheric pressure is to insert an open pipe
into the overflow line.

4. When water is being added to the mud, it should be added upstream of the
desilter in order to reduce the mud viscosity and improve efficiency of the
desilter. Chemicals, bentonite, or other mud additives should be added to the
system downstream of the desilter.

5. Air entrainment in the cone overflow will be reduced if the overflow line slopes
down at an angle rather than dropping vertically. This line should stop at the
surface of the mud in the tank. Note that the cones are designed to pull air into
the mud; thus air entrainment cannot be eliminated when using hydrocyclones.

6. When Barite is not the most valuable material in the mud, hydrocyclones may be
appropriate for solids control. For example, a 1.38 s.g. KCl/XC mud might
contain only $57/m
3
worth of barite and $125/m
3
worth of other additives. Use of
cones to remove some drilled solids and some barite might be cheaper than
diluting and rebuilding new mud.

7. When a weighted system is unacceptably abrasive, hydrocyclones may be run
for one or two circulations to strip out the sand.


11.3.6 Mud Cleaners

A mud cleaner is a device that has hydrocyclones mounted such that their underflow falls on a
fine-mesh vibrating screen. When operating properly, a mud cleaner combines the high
processing rate of the cones with the sharp cut and dry discharge of a vibrating screen.

The solids that leave the bottoms of the cones but do not pass through the screen are discarded.
The cone overflow and the material going through the screen are both returned to the active
system. Commercial mud cleaners are circular or rectangular in shape.
Most drilling operations restrict mud cleaner use to weighted systems, usually higher than
1250kg/m
3
. Most mass-balance studied, system evaluations and particle size analysis performed
by Anchor indicate that the actual low gravity solids removal "workshare" performed by mud
cleaners is not that impressive. When deciding on whether a mud cleaner should be used it is
important to select the proper screen size. Fresh unsheared barite in the system would require a
screen of about 150-200 (10474) mesh to be installed initially. This doesn't make much
sense if the shakers are equipped with 210 mesh screens.

After the barite has been sheared finer screens may be installed. At this point the screen
underflow should be analyzed to discern the value of the barite being recovered and the amount
of low gravity solids being returned to the system.


11.3.7 Decanting Centrifuges

Decanting centrifuges are an integral part of most solids control programs. New advances in
centrifuging technology have enabled some machines to rotate at 3,500+ RPM, generating a
force of over 2,000 times the force of gravity while feeding at 150 U.S. gpm. These parameters
enable centrifuges to separate solids particles down to 2 .

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Feed
Mud In
Solids
Effluent
Figure 11.3

Figure 11.3 shows a cutaway view of a centrifuge. Mud enters the machine through the feed pipe
on the right side. Often it is desirable to dilute the feed mud with water. This lowers the viscosity,
enhancing the efficiency of the machine, thereby lowering the cut point. If the feed mud is diluted,
mud and water must be metered in order to perform proper efficiency analysis.

Feed mud is discharged into the scroll feed chamber, where it is distributed to the scroll. The
mud is thrown outwards to the bowl, where its speed soon approaches that of the rotating bowl.
Note that the flights on the scroll do not touch the bowl. The space between the bowl and the
flights is called the clearance tolerance and is usually about 1/8". A cake of solid particles
occupies this space along the entire inside diameter of the bowl. This cake rotates at the same
speed as the bowl, with the bowl.

The liquid mud occupies a cylindrical space beginning at the cake and on towards the body of the
scroll. This fluid is referred to as the pond. The depth of the pond may be varied by adjusting
the height of the weirs at the liquid discharge end of the machine. The pond depth for most
machines varies from between 1.5" to 2.5". The length of the pond from the liquid discharge end
of the bowl to the point where it stops somewhere along the inclined or tapered part of the bowl is
called the clarification length. It is generally accepted that most solids separation occurs at the
surface of the pond. Solid particles are centrifugally forced through the pond toward the cake.

The bowl and the scroll both rotate in the same direction. All centrifuge specifications include a
gear ratio. In most machines the scroll turns slightly slower than the bowl. (If it didn't the flights
would rotate at the same speed as the cake.) Because the scroll rotates at a different speed, it
acts like a screw or auger. The effect is to cause the flights to move horizontally to the left in
relation to the bowl. As the flights pass by the cake they scoop solid particles from the surface of
the cake and augur them towards the solids discharge end of the machine.

Most machines are equipped with a gear ratio of between 50:1 and 80:1. When a machine has a
gear ratio of 50:1 it means that for every 50-bowl revolutions the scroll turns 49 times. To verify
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this, open the cover on the centrifuge and look through the solids discharge port at the tapered
end. Place a chalk mark on the flight, in line with a chalk mark on the bowl. Rotate the bowl by
hand one time. When the port returns after one revolution, the chalk marks will be separated by a
space of about 7. The sound emanating from most centrifuges oscillates. By counting the
number of oscillations in one minute and multiplying by the numerator in the gear ratio it is
possible to determine the RPM the machine is operating at.

The distance between the flights is called the pitch. This distance is usually 70 mm - 100 mm.
For each differential revolution the solids are transported along the cake a distance of 1 x pitch
length. Some scrolls have double lead flighting in which case solid particles are transported a
distance of 2x pitch per differential revolution. Some machines are manufactured with tungsten
carbide tiles on the tips of the lead flights. This is an excellent innovation since this is where most
of the wear occurs in the interior of the machine. In fact if the torque-actuated mechanism
(usually a shear pin) continuously triggers a shut down, it often means that the tips of the flights
are worn. The tips are tapered, and as they wear the clearance tolerance increases. This not
only increases the thickness of the cake, but also increases the contact area between flight and
cake. The resulting increase in friction is what usually causes the torque-activated mechanism to
trip.

The solids are augured along the length of the bowl toward the solids discharge ports. Eventually
they reach a point somewhere along the tapered (conical) part of the bowl where they leave the
effluent or pool. The area from the pool to the discharge ports is called the beach. It is here that
the solids reach a "dry" state. Increasing the pond depth can reduce the length of the beach. As
the length of the beach is reduced the solids discharge becomes wetter. The inclination of the
beach angle in almost all centrifuges is between 8.5 and 10.

The fluid, which leaves the machine, must flow between the flights in a direction counter to which
the flights are moving in relation to the bowl. That is to the left in figure 11.3. The flights act as
channels and the fluid spirals along the parameter of the inside of the bowl to the discharge
ports. This regime is called helical flow - common to most centrifuges.

The effluent capacity (pond volume) of most large bowl (14"x 48") centrifuges is about 10 - 13 US
gallons, depending on the pond depth. The retention time of any volume of liquid in the machine
is between 4 and 5 seconds depending on the feed rate. In other words the fluid moves through
the flights with enough velocity to be in turbulent flow if the viscosity isn't excessive. It has been
theorized that this turbulence could hamper separating efficiency by scooping solids from the
cake back into the effluent. As a result some manufacturers are providing flights with openings in
them such that the fluid may travel directly (and slowly) to the discharge ports - without having to
spiral along the outside perimeter of the bowl. This type of flow is called co-axial flow. The
internal flow regime does not effect effluent retention time.

Anchor Drilling Fluids has developed equations, which generate a theoretical cut point for any
given decanting centrifuge. Inputs into these equations include:

G Force Imparted
Particle Density
Fluid Density
Fluid Viscosity
Pool Depth
Flow Rate
Volume of fluid

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The following rules of thumb apply to centrifuging drilling fluids:

The most important parameter in centrifuging is the G Force a given machine can generate. G
Force can be calculated by:

G Force = 0.0000142 (RPM
2
) (Diameter - Inches)

The Diameter should be calculated from the surface of the pond on one side of the bowl to the
surface of the pond on one side of the bowl to the surface of the pond on the other side of the
bowl since the majority of separation occurs on the surface of the pond.

Decreasing the pond depth will make the solids discharge drier - the beach length is increased.
However this will also reduce the fluid retention time in the machine, reducing the allotted time for
a particle to separate (to reach the cake). This does not increase the cut point as dramatically as
one would expect. This is because the particle has less distance to fall through a shallower pond.

Increasing the feed rate substantially increases the cut point by reducing the fluid retention time.
Theoretically, increasing the feed rate from 100 U.S. GPM to 200 U.S GPM would increase the
cut point in a given machine from 3.45 to 4.90? ? ?all other factors being equal. Many drilling
people are concerned about the throughput capacity of centrifuges. Most machines are being
designed to process substantially less volume than the circulation rate. What they fail to
understand is that the solids processing rate of a given machine is a much more definitive
number. For example if the ROP in a 215.9 mm hole interval is 10 m/h, 950 kg of drilled solids
are being added to the mud system each hour. If the shaker is removing 800 kg/h, and the
centrifuge is removing 150 kg/h then the mud density will not increase, even if the centrifuge is
only processing 50 U.S. GPM.


11.4 SOLIDS IN DRILLING FLUIDS

11.4.1 Unweighted Systems

Solids control in unweighted systems is a logical exercise. The shale shaker screens are sized
such that the smallest possible screens are installed. The desander is operated usually if the
whole mud sand content exceeds 1/4% by volume, or if its underflow density is reasonably higher
than the active system density.

The desilter is normally run continuously - even while tripping. Its efficiency can be minimized by
calculating the number of kg of low gravity solids discharged per hour at different operating
pressures and aperture diameters. Before changing aperture diameters the L.G.S discharge for
two cones with different aperture sizes can be analyzed and compared on an individual basis.

The desilter discharge is usually directed into a catch tank where it is blended with the whole mud
feeding the centrifuge. This set up is called a closed loop system. Analysis should be performed
regularly on all equipment when running an unweighted system.


11.4.2 Weighted Systems

A weighted system usually has a density in excess of 1250 kg/m
3
. Again the smaller shaker
screen size is used. Desanders are not normally operated, unless on a one circulation-at-a-time
basis to control the sand at less than 1%. Often hydrocyclones are used also on a circulation
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basis - sometimes over screens - as mud cleaners. When the centrifuge is operated it is used to
recover barite in the underflow. The liquid phase is discarded.

Weighted systems have less tolerance for drilled solids. In highly weighted systems - above 2
000 kg/m
3
all of t